EPA-R2-73-167
Environmental Protection Technology Series
Biological Removal of
Carbon and Nitrogen Compounds
from Coke Plant Wastes
Office of Research and Monitoring
U.S. Environmental Protection Agency
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
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EPA-R2-73-167
April 1973
BIOLOGICAL REMOVAL OF CARBON AND
NITROGEN COMPOUNDS FROM COKE PLANT WASTES
By
John E. Barker
R. J. Thompson
Project 12010 EDY
Project Officer
Leon H. Myers
Petroleum-Organic Chemicals Wastes Section
Treatment and Control Research Program
Robert S. Kerr Environmental Research Laboratory
Ada, Oklahoma 74820
Prepared for
OFFICE OF RESEARCH AND MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
For sale by the Superintendent o^ DSoettSaeats'j W.S. Government Printing Office, Washington, D.C. 20402
Price &9$ flptticsttaWtpaid or $2.00 GPO Bookstore
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EPA REVIEW NOTICE
This report has been reviewed by the Environmental Protection Agency
and approved for publication.~ Approval does not,signify that the
contents necessarily reflect the views and policies of the-Environ-
mental Protection Agency^ nor does mention of trade or?commercial
products constitute endorsement or recommendation for use.
ii
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ABSTRACT
A one-year study of a biological process for treatment of coke plant
ammonia liquor was conducted. The process was designed to remove carbon
compounds and ammonia. The pilot plant consisted of three treatment
systems arranged in series. These systems were designed for the removal
of carbon compounds, the oxidation of ammonia to nitrate (nitrification),
and the reduction of nitrate to nitrogen gas (denitrification). The
study was jointly sponsored by the American Iron and Steel Institute,
the Environmental Protection Agency, and Armco Steel Corporation.
The results of the study indicate that the biological process can be
used to remove carbon compounds and ammonia from dilute ammonia liquor.
Treatment efficiencies obtained include removals of greater than 99.9
percent phenol, 80 percent COD and 90 percent ammonia. Removal efficiencies
for cyanide and thiocyanate were less encouraging with averages of 57
and 17 percent, respectively. At this time, the inability to efficiently
remove cyanide and thiocyanate raises a question as to the long range
applicability of the process to existing and proposed water quality
standards. ;
A complete evaluation of the capabilities and limitations of the system
was beyond the scope of this study. Additional development work will be
required before the process could be considered for commercial application.
iii
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CONTENTS
Section
I
II
III
IV
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
Page
CONCLUSIONS AND RECOMMENDATIONS 1
INTRODUCTION 5
DESCRIPTION OF PROBLEM 7
POTENTIAL SOLUTIONS TO PROBLEM 13
Modified Method of Coke Production 13
Quenching 14
Incineration J 14
Distillation 14 & 15
Deep Well Disposal 15
Removal or Recovery of Specific Contaminates 15
BIOLOGICAL OXIDATION AND DENITRIFICATION 27
Biological Oxidation of Coke Plant Wastes 27
Biological Nitrification and Denitrification 33
DESCRIPTION OF PILOT PLANT 39
SAMPLING AND ANALYSIS 45
OPERATIONS AND RESULTS 49
The Excess Ammoniacal Liquor 50
Carbonaceous Treatment Unit 52
Nitrification Unit 72
Denitrification Unit 82
SPECIAL STUDIES 91
Carbonaceous Unit 91
Denitrification Unit 94
COST ESTIMATES 97
ACKNOWLEDGEMENTS 103
REFERENCES 105
PUBLICATIONS 111
GLOSSARY 113
APPENDIXES
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FIGURES
No. Page
1 FLOW DIAGRAM BY-PRODUCT COKE PLANT 9
2 HYPOTHETICAL PATHWAYS OF NITRATE REDUCTION 35
IN MICRO-ORGANISMS
3 PILOT PLANT FLOW DIAGRAM . 41
4 SAMPLING POINT LOCATIONS 46
5 CARBON REMOVAL UNIT-PERCENTAGE OF WASTE UNDER 57
TREATMENT
6 CARBON REMOVAL UNIT-INFLUENT CONCENTRATIONS, 59
ORGANIC CARBON AND COD
7 CARBON REMOVAL UNIT-INFLUENT CONCENTRATIONS, 60
PHENOLICS
8 CARBON REMOVAL UNIT-INFLUENT CONCENTRATION, 61
THIOCYANATE
9 EXCESS AMMONIA LIQUOR-CONCENTRATIONS, TOTAL 62
NITROGEN AND AMMONIA
vi
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TABLES
No. Page
1 TYPICAL QUANTITIES OF VOLATILE PRODUCTS PER 8
,-TON OF COKE
2 TYPICAL ANALYSIS OF AMMONIACAL LIQUOR AND STILL 10
WASTE
3 PILOT PLANT EQUIPMENT 42
4 SAMPLING AND ANALYSIS SCHEDULE 47
5 EXCESS AMMONIACAL LIQUOR 51
6 SUMMARY OF CHARACTERISTICS - EXCESS AMMONIACAL 52
LIQUOR
7 OPERATING CONDITIONS, CARBON REMOVAL UNIT 54
8 INFLUENT, CARBON REMOVAL UNIT 55
9 LOADINGS AND REMOVALS, CARBON REMOVAL UNIT 56
10 EFFLUENT LOADS PER UNIT VOLUME OF WASTE 66
11 SUMMARY OF CONDITIONS DURING PERIODS OF UNIT 70
STABILITY
12 SUMMARY OF TREATMENT MIT FAILURES 71
13 OPERATING CONDITIONS, NITRIFICATION UNIT 74
14 NITRIFICATION UNIT, SUMMARY 77
15 OPERATING CONDITIONS, DENITRIFICATION UNIT 78
16 OPERATING RESULTS, DENITRIFICATION UNIT 85
17 DENITRIFICATION - STOICHIOMETRIC COMPUTATION 87
18 PRETREATMENT OF EXCESS AMMONIACAL LIQUOR, 92
PERCENT REMOVALS
19 BIOLOGICAL REMOVALS FRO?! PRETREATED WASTE 93
20 CAPITA!, COST E.A.L. BIOLOGICAL TREATMENT 98
21 OPERATING COST BIOLOGICAL TREATMENT 100
22 COST COMPARISONS OF NITRIFICATION CHEMICAL 101
REQUIREMENTS
23 COST COMPARISON OF ORGANICS FOR DENITRIFICATION 102
vii
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SECTION I
CONCLUSIONS AND RECOMMENDATIONS
After nearly one year of pilot plant operation, it is concluded that
carbon compounds can be biologically removed from diluted ammonia
liquor. Although this project demonstrates that ammonia can be
partially removed by biological oxidation, it failed to demonstrate
consistent removal of ammonia to the degree necessary for the
effluent standards, currently under consideration by regularoty
authorities. The cost per unit of ammonia removal compared to other
processes casts doubt on the commercial feasibility of this aspect of
the process. Three stages of treatment are required. These treatment
stages are carbon removal, nitrification and denitrification. The
three biological processes must be arranged in this order if effective
treatment is to be achieved.
Unanticipated delays and system upsets caused primarily by rapid
fluctuations in ammonia liquor strength prevented the complete evaluation
of important process requirements particularly for the nitrification
system. Some of the more important parameters not completely defined
are waste loading, temperature, and sludge wasting requirements. These
parameters have a significant effect on the size, efficiency, and cost
of biological treatment systems. Additional development to evaluate and
define the effect of these design parameters will be required before the
system could be considered for commercial application.
Several specific observations and conclusions were made during the study.
These are as follows:
1. The strength of ammonia liquor is highly variable. Fluctuations
by factors of three or more in concentration of many constituents
were not uncommon. This variability must be eliminated or
dampened if stable and efficient biological treatment is to be
achieved.
2. Utilizing an aeration time of 24 hours and temperatures between
75 and 90°F, the carbonaceous removal unit treated diluted excess
raw ammonia liquor at influent concentrations of chemical oxygen
demand of 3000 mg/1 and phenolics of almost 600 mg/1. Removals
of essentially all of the phenolics and about three-quarters of
the COD were experienced. Operation is improved by the higher
temperatures.
3. Thiocyanate, a major component of ammonia liquor, was only partially
removed by the carbonaceous removal unit even at very low unit
loadings. Apparently, during most of the experiment conditions were
not conducive to the proliferation of organisms capable of oxidizing
thiocyanate. Residual thiocyanate in the carbonaceous units effluent
is a major contributor to residual COD.
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4. Cyanide removal was quite erratic with removal efficiencies
averaging only 57 percent. Fluctuations in cyanide removal
were generally unpredictable and inconsistent with waste
strength.
5. At low unit loadings, significant nitrification of ammonia was
measured in the carbonaceous treatment stage.
6. During one part of the study, the carbonaceous unit efficiently
removed COD and phenol while operating in a mode similar to an
aerated lagoon.
7. The carbonaceous unit experienced aerator foaming problems which
increased with increasing waste strength. Tributyl phosphate
was an effective control.
8. Major problems encountered by the carbonaceous unit included
variability of loadings resulting from inconsistencies' in the
raw waste, both high and low reactor temperatures, high reactor
cyanide and thiocyanate concentrations, and low reactor dissolved
oxygeii levels.
9. Nitrifying organisms are quite sensitive to many constituents in
ammonia liquor. Dilution and efficient operation of the carbonaceous
unit are necessary to prevent inhibition and loss of nitrification
efficiency.
10. Nitrification efficiency reached 90 percent oxidation of ammonia
when the waste was diluted to 12 percent strength and the carbon
removal unit was operating satisfactorily.
.,-•
11. Additions of agents to supply inorganic carbon for metabolism
of the autotrophic nitrifiers and an alkaline agent to neutralize
the acidity produced in the process are necessary. The most
practical chemical system is sodium carbonate and hydrated lime.
12. Nitrification was found to proceed satisfactorily x^ithin the pH
range of 6.8 to 8.2 and that temperatures of 90-95 F were much
better than 80-85°F.
13. The maximum observed rate of increase in oxidized nitrogen was
150 mg/1 of nitrogen per day. This may give some measure of the
rate of response of the unit to increases in influent ammonia
concentration.
14. The major operational problems of the unit resulted from poor
quality carbonaceous unit effluent, high nitrification unit pH
and low nitrification unit temperature.
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15. The major biochemical reactions occurring within the nitrifi-
cation unit lead to the oxidation of ammonia to nitrite and
nitrate, the reduction of oxygen, and the reduction of carbon
dioxide.
16. No overall loss of nitrogen took place within the first two
operational units of the pilot plant.
17. The denitrification unit was capable of removing 95 to 100
percent of the oxidized nitrogen at influent concentrations up
to 600 ppm.
18. Temperature variations between 70 and 90°F had no observable
effect on denitrification efficiency.
19. Alkalinity and pH control were not necessary at oxidized nitrogen
removals up to 600 ppm.
20. Sludge bulking in the denitrification unit final clarifier was
a problem. Flotation should be considered for solids separation
in this system.
21. Molasses proved to be an acceptable reducing agent for denitri-
fication. Dean, et^ al_t has suggested methanol as a reducing
agent. From an economic standpoint, methanol which costs twice
as much as molasses is considered second choice.
22. Careful control must be exercised to maintain a reasonable balance
between oxidized nitrogen and the reducing agent. The recommended
dosage of reducing agent in terms of mg/1 of chemical oxygen
demand was found to be equal to about 9 times the sum of the
milliequivalents per liter of nitrite and nitrate to be reduced.
23. The complete three-stage treatment plant under optimum operating
conditions should be capable of removing well over 99 percent of
the phenolics, 90 percent of the organic carbon, 70 percent of the
chemical oxygen demand, and 90 percent of the ammonia.
24. Preliminary estimates for a treatment system sized for a 33,000
TPM coke plant are $995,000 capital cost and $230,500 annual
operating cost. The operating cost represents $15.78 per 1,000
gallons of excess ammonia liquor or $0.58 per net ton of coke.
Seventy to eighty percent of this cost is for ammonia removal.
The results of this study strongly suggest that a full-scale biological
system to remove carbon compounds from excess ammonia liquor could be
designed and built. It also indicates that additional development is
required to enable the construction and operation of a reliable, full-
scale, biological system for removal of the ammonia.
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It is recommended that future research and development efforts be
directed at defining the causes and developing methods to eliminate the
rapid fluctuations in ammonia liquor strength; defining the parameters
required for biological removal of cyanide and thiocyanate, and optimizing
the system for their removal; and evaluating the aerated lagoon as an
alternate to the activated sludge process.
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SECTION II
INTRODUCTION
The operation of by-product coking facilities results in the discharge
of nutrients, oxygen consuming materials, and toxic substances to the
nation's lakes and streams. This is one of the major unsolved water
pollution problems facing the steel industry. The problem is magnified
by the concentration of coke production in small areas of the United
States. Seventy percent of the producing facilities are located in the
states of Pennsylvania, Indiana, Ohio, and Alabama. An additional 20
percent are distributed among five northeastern states. And the
remaining 10 percent are scattered across the country in widely-separated
locations. The large production of coke, the concentration of coking
facilities, and the increasing requirements for water pollution control
necessitate the development of a practical method for the treatment of
coke plant wastes. Although a considerable amount of research has been
conducted, the complexity of the wastes has prevented the development of
a practical disposal technique.
Recognizing the need for a practical method for the disposal of coke
plant waste, the American Iron and Steel Institute (AISI) initiated a
laboratory study in 1968 to determine the applicability of biological
treatment to this problem. The AISI Water Resources Fellowship at
Carnegie-Melion University were responsible for this study. From the
beginning, it was recognized that several treatment stages would be
required. These stages would include carbonaceous removal, nitrification,
and denitrification. The treatment stages were arranged in this order to
prevent inhibition of the nitrifying bacteria by excessive amounts of
organic carbon. Preliminary results from the laboratory pilot plant study
were quite encouraging with excellent removals of phenol and ammonia.
On the basis of these preliminary laboratory results, it was decided to
conduct a field scale pilot plant study concurrent with the laboratory
study. The principal objectives of the study were to determine the
technical and economic feasibility of biological treatment of excess
ammoniacal liquor. In addition, the effect of various controllable
parameters on process efficiency were to be evaluated.
The pilot plant was built at Armco Steel Corporation's Houston, Texas
Works. At this location, an existing by-products coke plant supplied a
continuous source of waste. The pilot plant was designed as three
completely mixed activated sludge plants in series with a maximum capacity
of one gallon per minute. The system started operation in January, 1970
and the study was terminated in January, 1971. The results of this one
year pilot study including the results of the concurrent laboratory
study are presented in this report.
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SECTION III
DESCRIPTION OF PROBLEM
Coke is a necessary intermediate product in the manufacture of steel.
The importance of coke in steel production is derived from its strength
as a reducing agent, its physical characteristics, and its low cost.
Coke is used as a reducing agent in the blast furnace where iron ore is
converted to molten iron or "hot metal." The hot metal is further
refined in open hearth, basic oxygen, or electric furnaces to steel.
The present United States coke production is approximately 60 million
tons annually. This production is expected to increase essentially at
the same rate as steel production, at least during the next one to two
decades. At present, more than 98 percent of all United States coke or
59 million tons annually is produced in by-product coke ovens.
The coking operation may be described as a process for the destructive
distillation of coal to produce a coke with satisfactory chemical and
physical properties for use in metallurgical applications.
The by-product coke oven is a long and narrow chamber, built in batteries
usually consisting of 10 to 100 ovens. The ovens are heated by the com-
bustion of gas evolved from their own charge of coal. Prior to use, the
gas is thoroughly cleaned and stripped of certain by-products by a series
of cooling and scrubbing operations. The by-products usually recovered
are gas, tar, ammonia, and light oil. Many secondary by-products are
obtained from the light oil at separate plants. The pollution problems
from the production of these secondary products are a considerably
different problem and usually of only minor concern.
The crude gas, e.g., volatile products leaving the ovens is composed of
the permanent gases whose mixture constitute the clean coke oven gas, in
addition to gases or vapors of water, tar, ammonia, phenol, hydrogen
sulfide, hydrogen cyanide, light oil, and naphthalene. Typical produc-
tion rates of some of these materials are shown in Table 1. Many of
these materials must be removed from the coke oven gas prior to use in
order to prevent excessive plugging and corrosion of the distribution
system. It is these gas cleaning and by-product recovery systems that
produce the contaminated waste water.
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TABLE 1
TYPICAL QJJANTmES ^FljyOLATILE J^QgJgTS^XER JTON^OF COKE
Gas 15,000 ft. 3
Tar 10 Sal-
Light Oil 4 8al-
Ammonia 7 lbs-
Phenolics °-6 lbs-
Hydrogen Sulfide 8 lbs.
Naphthalene 1-5 lbs.
The gas cleaning and by-products recovery system most widely used in the
United States is the semidirect system. There have been a number of
other systems proposed, some of which have been tried, and at least one
of which, the indirect recovery system, is in full-scale operation. The
principal differences between these alternate systems is the method of
ammonia removal and the type of by-product ammonia recovered; i.e.,
ammonium sulfate, diammonium phosphate, or ammonium hydroxide. Figure 1
is a flow diagram of the semidirect system.
In the semidirect system the crude gas leaves the ovens through stand-
pipes at the top, which connect to a large collecting main traversing
the full length of the battery. The gas receives its first cooling in
the collector main by contact with sprays of ammoniacal liquor which was
previously condensed from the gas. This initial cooling results in the
removal of approximately 85 percent of the tar. The gas then passes
through the primary cooler where the remaining 15 percent of the tar is
removed. The primary cooler may be the direct or indirect type.
From the primary cooler, the gas passes through the tar extractor, an
electrostatic precipitator, for removal of the last traces of tar.
Condensate drains are provided at each piece of equipment from the
collector main through the tar extractor. The condensate is sent to
decanter tanks for separation of the tar. The recovered tar is used as
fuel in the steel plant or sold to local chemical companies for the
manufacture of a variety of secondary by-products. The tar-free liquor
is pumped back to the collector main. Excess amraoniacal liquor resulting
from condensation of gas moisture is sent to an ammonia still.
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TO < FKtoM
RIVER _, -DRIVER
FUUSMIMQ
LIQUOR
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|l
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1
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*
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RES6R- JiJ| L— ,
VOIR. 1 ' II
STEAM 111
AMMONIA
STILL,
STILL,
WASTE
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.E 1 \
r
i
•
t
COOLING
— ^^TEB. <%*
II .STORAGE
r^'^ '_» 6Ag| !=5r
r.c 1 WASH 0
FINAL SCRURBERr=::FRoM
COOLER, SCRURBER BEHTO,
±S. PLAWT
""" Hi i ^ll
t "*
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. INAPHTHALENE TO
n SKIMMER BENWU
BASIN PLANT
ill MA PUT HALEM6
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WATER
J
=IHAL COOLIM<3>
YSTEM OVERFLOW
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FLOW DIAGRAM To SE'WER
SEMIDIRECT BY-PRODUCT COKE PLANT
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The volume of excess ammoniacal liquor is dependent upon coal moisture
content and varies from 30 to 35 gallons per ton of coke. This liquor
contains (Table 2) a large percent of the total volatilized ammonia,
nearly all of the phenol, and significant but unrecoverable quantities
of cyanide, thiocyanate, sulfide, and chloride.
TABLE 2
TYPICAL ANALYSIS OF AMMONIACAL LIQUOR AND STILL WASTE
Excess * Undephenolized (1) Dephenolized (1)
Ammoniacal Still Waste Still Waste
Liquor . ^
Cone. Discharge Cone. Discharge , Cone. .Discharge
(ppm) Ib./lOOO (ppm) Ib./lOOO (ppm) Ib./lOOO
tons coke tons coke tons coke
Ammonia 3800 1300 155 77 110 , 50
Phenol 1500 500 1320 725 158 71
Cyanide 20 7
y.
Thiocyanide 600 200 -
Sulfide 2 ' 1 -
e
Chloride 7000 2300 4350 2393 5400 2930
Volume
5>
(gal./ton coke) 33 55 45
* Based on analysis from Armco Steel Corporation's Houston Coke Plant
.Ammonia in the excess liquor is volatilized by live steam injection in
the ammonia still. The volatilized ammonia is reinjected into the gas
stream following the tar extractor. The gas is then scrubbed with
sulfuric acid in the saturator for removal of ammonia as ammonium
sulfate.
The waste water from the ammonia still is either dephenolized and dis-
charged to a receiving stream or disposed of without dephenolization
usually by evaporation at the quench station. Two dephenolization
processes are in common use today. The most modern and efficient
10
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system is the liquid extraction process where benzol or light oil is
used to absorb the phenol. It is later removed from the absorbent by
caustic extraction to form a sodium phenolate by-product. The other
dephenolizing system is the vapor recirculation process x^here the phenol
is vaporized with steam. The steam and phenol vapors are then contacted
with caustic to form sodium phenolate. Although these processes are
quite efficient, the waste water discharged to the receiving stream still
contains excessive amounts of phenol, ammonia, and cyanide.
Complete elimination of the water waste from the ammonia still can be
accomplished by evaporation at the coke quench station. Although this
method is rather widely used, it is an undesirable approach because of
problems with corrosion of the tower, quench car, and local buildings
and equipment. These problems are a result of the chlorides in the
still_waste.
Following the saturator the gas is cooled in the final cooler in preparation
for light oil removal. Light oil is scrubbed from the gas by a high
boiling wash oil in the gas scrubber. The light oil is then distilled
from the wash oil and the wash oil is recirculated. The light oil is
refined in the benzol plant by distillation and fractiohation into
benzol, toluol, and xylol. The gas is then ready for distribution.
By-product ammonia recovery from coking operations was a profitable busi-
ness in the early 1900's. Since that time, an economical process for
the synthesis of anhydrous ammonia has been developed. The use of this
process has resulted in the steadily decreasing value of ammonium sulfate
as well as other ammonium compounds. Today, the cost to produce ammonium
sulfate is higher than its market value and in many locations there is
virtually no market. In general, by-product ammonia recovery in American
coke plants is no longer considered a profitable venture. At best it is
an expensive pollution abatement measure. For this reason, emphasis on
efficient operation of by-product recovery equipment in many plants has
been reduced resulting in significant increases in the discharge of
ammonia, phenol, and other materials as listed in Table 2. In other
plants, the ammonia recovery equipment has been completely abandoned
resulting in the direct discharge of ammoniacal liquor, and the required
conversion of the final cooler to a once-through system.
The high cost of by-product ammonia recovery, as well as other available
treatment and disposal systems and the inability of these systems to
produce acceptable effluent quality at many locations, has resulted in
the need for alternative pollution control methods. It is the purpose
of this study to evaluate one such alternative—biological treatment.
11
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SECTION IV
POTENTIAL SOLUTIONS TO PROBLEM
Many mechanisms have been considered to eliminate or reduce the amounts
of ammoniacal liquor and for its treatment or disposal. This section
will briefly describe some of the treatment or disposal methods other
than microbiological that have been considered. Biological methods will
be reviewed in the succeeding sections.
MODIFIED METHOD OF COKE PRODUCTION
Ammonia liquor itself is an outgrowth of changing technology in the
manufacture of coke. At one time, the major source of coke in this
country was from beehive ovens. These devices manufactured coke but no
by-products and used the evolved gases to heat the oven by burning the
gas within the oven itself. Thus, at no time was the gas allowed to cool
and formation of ammoniacal liquor was avoided. However, because of air
pollution problems and the desire to recover by-products and the sas
itself, these units were replaced by the currently used slot-type ovens
with the ammoniacal liquor problem. Currently, operational changes are
being proposed which may reduce the amount of ammoniacal liquor produced
and new coking techniques are proposed which may eliminate the problem.
One change which may reduce the quantity of ammonia liquor is to predry
the coal prior to charging. This is a part of a new system being
developed for smokeless charging of slot ovens. If the vapors evolved
during predrying are not heavily contaminated and do not present a
problem of disposal in themselves, then this would obviously reduce the
quantity of waste. In addition, this might effect the amounts of other
constituents, especially ammonia. Ammonia is known to be protected
from thermal cracking by the presence of such oxygenated compounds as
water. In fact, at one time, when ammonia was a valuable by-product of
coking, steaming was considered as a method to enhance the yield. Con-
versely, it might be anticipated that less coal moisture would lead to
reduced amounts of ammonia.
For several years, the coking industry has'been seeking new methods for
making coke. Currently, several continuous coking processes (2) are
under development. The major attributes of these processes, according
to their developers, is that they can coke coals that cannot be processed
in the current slot-type ovens and that they reduce air contamination.
No information on potential vrater pollutants is known; and until defini-
tive information is available, the presumption must be made that problems
equal to those in slot-type ovens will exist. However, it can be hoped
that continuous coking of predryed coal may lead to a lower potential for
water pollution.
13
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QUENCHING
After the coal has been carbonized, the hot coke is removed from the oven
and is cooled by direct water sprays. This process is called quenching.
Coke quenching as presently practiced uses about 500 gallons of water per
ton of coke quenched with a loss of about 150 gallons per ton through
evaporation. Some coke plants have utilized this evaporative loss to
dispose of ammoniacal liquors as well as other wastes.(1» 3)
A major problem with the use of highly saline waste, such as ammoniacal
liquor for quenching is the increased rate of equipment corrosion. The
costs incurred from this corrosion are generally high and must be con-
sidered as part of the costs of disposing of ammoniacal liquor.
The concept of coke quenching as a method for the disposal of ammoniacal
liquor was based on the supposition that the potential contaminating
constituents of both air and water were burned by the heat from the coke.
Unfortunately, however, instead of being destroyed, the volatile con-
stituents are simply distilled and discharged to the atmosphere. This
has been proven in the case of phenolics in one quenching operation (4)
and while not as definitive, some information is available which indi-
cates that sizeable amounts of the ammonia in the quench water is also
released to the atmosphere. (5) xhe fate of these materials after
release is not known. In certain instances, this process has been sus-
pected of contributing to air pollution.
INCINERATION
Incineration has been considered as an optimum disposal method for many
kinds of waste products including concentrated liquid wastes. For
aqueous wastes, in general, the major economic consideration is the dif-
ference between the energy requirements for evaporation of the water and
the energy recovered by combustion of the waste constituents. In the
case of ammoniacal liquors, an additional problem is encountered. That
is one of equipment corrosion resulting from the high inorganic chemical
content (especially chlorides) of the waste. No doubt, incineration of
this waste is technologically possible, but in light of the decreasing
availability and the resultant increasing cost of fossil fuel, the
desirability and the economic feasibility is seriously questioned.
Rudolfs *• ' reports that one installation in Germany evaporates and burns
the residue. All of the waste water is evaporated directly into the air
by gas-heated furnaces and most of the phenols were burned in the 250-foot
furnace stack. Increased equipment corrosion is said to result.
DISTILLATION
The major conceptual difference between simple evaporation and distil-
lation is that in distillation the vapors are recondensed while in
evaporation the vapors are usually discharged directly to the atmosphere.
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The equipment is generally much more complex for distillation than for
evaporation but distillation lends itself better to both thermal and by-
product recovery. Distillation, as a method for treating coke plant wastes,
is not new and is currently the method of choice at many plants for removal
of ammonia and phenolics from ammoniacal liquors. These specific processes
will be covered later in this section.
One proposed process ^s stated to treat completely a conventionally free
ammonia distilled and dephenolized liquor by a modified distillation process.
The liquor is distilled to a dry powder after addition of acid to retain the
ammonia and activated carbon to retain the phenolics in the residue. The
process appears to be fairly complex and no actual applications of the pro-
cess are known.
i . ..
The use of deep injection wells for the disposal of wastewaters has grown
rapidly in recent years. The advantages of this method of disposal as
delineated by its proponents include: (1) complete disposal of waste;
(2) minimum pretreatment needed; (3) no complicated equipment required; and
(4) low operating cost. For coke plants located in a suitable injection
area, disposal of ammonia liquor to a deep well is possible. Care would
be required in the ,; pretreatment step to assure the complete removal of tars
and other suspended materials that might clog the aquifer. The compatibility
of waste with the aquifer also needs to be carefully evaluated because of the
many potential reacting chemical species involved. Two wells are known to
be in operation for disposal of ammoniacal liquor. One of these wells is
operated by Ford Motor Company in Detroit, Michigan, and the other is
operated by Bethlehem Steel in Indiana.
Currently the use of injection is being reviewed from both a technological
and legal framework and the future use of this process is being seriously
questioned.
REMOVAL OR RECOVERY OF SPECIFIC CONTAI'IINATES
Most wastes are treated by methods which selectively remove specific con-
taminating substances which prepares the waste adequately for disposal,
reuse, or further treatment. The contaminates of major concern in coke
plant wastes are divided into two major categories; e.g., carbonaceous and
nitrogenous compounds. The carbonaceous constituents of major concern have
been phenolic in nature and much of the work has been directed toward the
removal of this group of compounds. However, in certain instances, the
removal of a broader variety of carbonaceous constituents is necessary and
more general methods have been developed. The Nitrogenous constituent of
major concern has been ammonia. The discharge of excessive amounts of
ammonia to receiving waters can interfere with established beneficial uses
for that water. Among the problems that have on occasion been attributed
to ammonia are fish kills, stimulation of algae growth, interference with
water disinfection, receiving stream oxygen deficiencies, and corrosion of
copper pipes. Several somewhat specific methods of treatment have been
developed for these constituents and the major ones of these will be re-
viewed briefly in the succeeding paragraphs.
15
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Dephenoli zatipn
Dephenolizatlon (D or removal of phenolics from ammonia liquor for recovery
purposes is widely practiced in this country. The two major methods in
use are liquid extraction and vapor phase recirculation. In liquid extrac-
tion, a solvent is used to extract the phenolics from the ammoniacal liquor
prior to ammonia distillation. A substantial part of the phenol is removed
from the solvent by distillation or by extraction with strong caustic soda.
The latter is preferred in this country. In the vapor recirculation process,
water vapor is recirculated upward through a tower having two or three sec-
tions in series. The vapor first passes through one or two caustic soda
scrubbing sections where it is freed of phenols, then on up the tower through
the hot ammoniacal liquor from the free leg of the ammonia still. The vapor
removes most of the phenols that remain in the liquor, then passes through a
duct and blower to reenter the caustic soda section of the cycle. Neither
system can be expected to remove more than 95-98 percent of the phenolics.
The resulting dephenolized liquor may not be suitable for discharge in all
instances.
Chemical Oxidation^of Phenol
An excellent report (8) on the results of laboratory and pilot plant experi-
ments has been prepared for the Ohio River Valley Water Sanitation Commis-
sion. This study on the oxidation of dephenolized ammoniacal liquors used
chlorine, ozone, and chlorine dioxide. The wastewater treated contained
from 30 to 300 mg/1 phenolics, 300 to 400 mg/1 of 5-day biochemical oxygen
demand, and oxygen consumed (dichromate method) values of 1400 to 1800 mg/1.
Removals of 60 percent of the BOD and OC were reported. Data shows that
any of the oxidants tested could be used to remove phenolics. Approximately
the following amounts of oxidant were required per mg/1 of phenol to remove
90 percent of the phenolics when starting at levels above 100 mg/1: 30 mg/1
for chlorine; 10 mg/1 for chlorine dioxide; and, 4 mg/1 for ozone. The
major problem with chlorine was the apparent necessity to satisfy the ammonia
demand prior to any oxidation of phenol.
Absorption of Organics
The removal of organic constituents in ammoniacal liquors by absorption on
activated carbon was used in Germany in 1930.(9) in this plant, clarified
carbonization wastewaters (coke filtered) was passed through beds of activated
carbon. Effluent phenol concentrations down to 50 mg/1 were reported.
Other organics were also removed. When the activated carbon had taken up 6
to 10 percent by weight of phenolics, it was washed with benzene to remove
phenolics and regenerated with steam. The phenolics were recovered by
distilling the benzene. This plant apparently did not operate very long
because of a drop in the price of phenol. A possible problem given in the
cited reference concerns reactivation difficulties resulting from high boiling
acidic and tarry constituents. Blackburn (10) and Ackeroyd (11) refer to
operational plants using activated carbon in England. Regeneration is again
with benzene and problems with tars have been reported. The Pittsburgh Coke
and Chemical Company is reported (D to have conducted a series of tests
prior to 1950 using activated carbon but problems with regeneration were
experienced.
16
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Currently a renewed interest has been shown in the use of activated carbon
to remove phenolics and other organics from ammoniacal liquors. The
Calgon Corporation of Pittsburgh, Pennsylvania, has been testing and pro-
posing a system including preclarification, absorption on a moving-bed of
activated carbon, and thermal regeneration of the carbon. Several com-
panies are considering this system but none is operational.
By-Product Production of Ammoniacal Compounds
The free ammonia in coke gas and the free and fixed ammonium compounds in
ammoniacal liquor are frequently recovered, usually by the semidirect pro-
cess as ammonium sulfate by bubbling the gas through a dilute sulfuric acid
solution in the saturator. The crystals of ammonium sulfate are separated
from the acid solution by means of a large basket centrifuge and are some-
times further dried in rotary dryers.(2) This process is widely used in
the United States; however, the value of the sulfate has decreased in
recent years to the point where it is no longer economical.
Theoretically, nitric acid would be an excellent absorbent for the recovery
of ammonia from by-product gases, and the resulting ammonium nitrate would
be a valuable material for both the fertilizer and explosive industries.
Here again, however, the recovery cost exceeds market value of the by-product.
Ammonium thiocyanate has been produced from coke-oven gas by scrubbing the
hydrogen cyanide in the gas with ammonium polysulfide solution.
NH3 + IICN + S = NH4SCN
In this process only the ammonia equivalent to the hydrogen cyanide content
is removed. This amounts to about 20 percent of the total ammonia in the
gas.
It would be ideal if economical methods were found whereby ammonia could be
removed from coke-oven gas and subsequently recovered from the absorption
system to yield a concentrated stream of gaseous ammonia which could then be
condensed to anhydrous ammonia or processed further to any desirable ammonia
chemical or derivative. At present, ammonia is being removed from by-product
gases by three methods: (1) by absorption in sulfuric acid to produce
ammonium sulfate; (2) by absorption in phosphoric acid to produce mono- or
diammonium phosphate; and (3) in liquor plants by absorption in water to
yield a dilute ammonia solution from which the ammonia is steam-stripped
and reabsorbed to yield a concentrated 30% ammonium hydroxide solution sold
as B liquor.(12)
The most promising of these chemical processes is the ammonium phosphate
system. This method involves the absorption of ammonia in an aqueous
solution of monoammonium phosphate which produces a solution of diammonium
phosphate. The solution is subsequently regenerated by heating, which
strips the ammonia, and restores the monoammonium phosphate solution.
17
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H NH4
NH. - PO. + NH ^- NH - PO
4 i 4 3 4 / . 4
H
Two processes have been proposed which involve absorption of ammonia to form
ammonium sulfate and subsequent decomposition of the ammonium sulfate to
yield a concentrated ammonia gas stream. One of the processes involves the
decomposition of ammonium sulfate in the presence of zinc oxide in a moving
bed system. In the upper part of the reactor ammonium sulfate is decomposed
at 500°C to form zinc sulfate and ammonia according to the following overall
reaction ,
(NH4) 2S04 + ZnO - 5 — ZnS04 + 2NH3 + 1^0
In the lower section of the moving bed reactor, the zinc sulfate is decomposed
at 850-1000°C according to the following reaction
ZnS04 - »— ZnO 4- SO
*.
The 803 is converted to sulfuric acid which is used to absorb more ammonia
and the ZnO is recycled with fresh ammonium sulfate.
The second process developed by Inland Steel involves the absorption of
ammonia in ammonium bisulfate solution according to the following reaction
The dried ammonium sulfate crystals are fed to a decomposition chamber heated
to 650°F in which the fused ammonium sulfate is decomposed to gaseous ammonia
and molten ammonium bisulfate according to the following reaction
2S04 - ^~- NH3(g) + N
The resulting ammonium bisulfate is recycled. The ammonia gas can be converted
to anhydrous ammonia gas or absorbed in water to produce an aqueous ammonia.
This process, while interesting, raises certain questions, llolten ammonium
bisulfate was found to be extremely corrosive to a wide varietv of metals.
18
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Incineration of Ammonia
The Koppers Company has proposed a system for destroying ammonia in
which the ammonia is absorbed from the coke-oven gas by water-scrubbing.
The weak liquor is stripped with steam to obtain a concentrated stream
of gaseous ammonia which is burned destructively.(12' Also described in
a U.S. Patent (13) is a process of burning the stripping ammonia in a
regenerator (part of the coke oven) at about 1200°C. Private correspon-
dence (14) containing a report by R. E. Muder entitled, "Oxides of
Nitrogen from Burning of Ammonia" presents his analysis of the proposal
to dispose of coke plant ammonia by combustion. He concludes that
burning of ammonia will not contribute any greater concentration of NO
to the atmosphere than will normal gas combustion.
A brief study of the thermodynamics of the formation of nitric oxide
during the combustion of ammonia has been made. (I-*) Thermodynamic data
were obtained from U.S. Bureau of Mines Bulletin 605 (1963). The stable
compounds formed during the combustion of ammonia are nitrogen and water.
The only oxide of nitrogen that may be formed in small amounts is NO.
Since nitrogen and oxygen are present during any combustion involving
air, there is no thermodynamic reason why more nitric oxide should form
when burning ammonia than when burning any other compound in air at the
same temperature. If nitric oxide is formed in objectionable amounts,
it could only be due to kinetic reasons. NO might be formed as an
intermediate during the combustion of ammonia and might not be given a
chance to reach equilibrium, which is unlikely. The equilibrium amount
of NO formed increases with increasing temperature. Hence a cooler
flame will minimize the formation of NO. A U.S. Patent granted to
Rosenblatt and Cohn (!*>) deals with the combustion of ammonia
+ 30_ - 2N, + 6H_0
J i 2. 2.
The reaction is accelerated at temperatures greater than 500°C using a
precious metal catalyst.
Ca ta1 ytic Decomp os i tion of Ammonia
There is good reason to believe that techniques could be developed to
destroy the ammonia by catalytic decomposition either in the coke oven
or in the by-product stream.
The literature on the behavior of ammonia, its synthesis and decomposi-
tion is extensive. Recent reports by Samples, McMichael, Vigani and
Arthur D. Little, Inc., give numerous references and an extensive review
of the subject. (12., 17, 13, 19)
19
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Ammonia is not a heat stable compound and at high temperatures will
dissociate into its elements, hydrogen and nitrogen, according to the
equation
The rate of decomposition can be increased with certain catalysts. A
number of catalysts exist. The most common catalysts are iron oxides.
Considerable insight into the mechanism can be obtained by comparison
between heterogeneous and homogeneous reactions with regard to the
respective energies of activation. The activation energy for ammonia
decomposition on a tungsten surface is about 41 kcal at 1043°C and more
than 80 kcal without a catalyst at a temperature of 1200°C.(10)
The primary mechanism of ammonia decomposition on iron oxide can be
shown as a two-step process: (1) chemisorption of ammonia on the iron
catalyst to form iron nitrides and liberation of hydrogen, and (2) the
subsequent desorption of nitrogen from the catalytic surface. From
studies (20, 21) ±t ±s proposed that the rate-determining step for the
decomposition reaction is the desorption of nitrogen.
H H
_l I
2NH v ^=""2NH^==5=r 2NH + 2H ^ ^ N - N + 4H
* * * * * *
«t "—. N • N + 6H •u ~* ' N + 3H,
* * * / /
Represents a single absorption sight.
White and Melville (22) did some laboratory tests at the University of
Michigan on the thermal decomposition of ammonia in the presence of other
gases. This early work was done without the intentional addition of any
catalytic agent and consequently, serves as a basis from which to start
other studies. At 685°C with the following flow rates in cm3/min,
H20 = 4.0, CO = 22.6, NH^ = 90.4 the ammonia decomposition was 27 percent.
From the geometry of the system, the estimated retention time in the
heater at 100 cm3/min is about 11 seconds. Other of their tests show
that at one atmosphere of pressure, pure ammonia, ammonia with hydrogen,
and ammonia with nitrogen decompose at the same rates. Some test runs
using a porcelain tube instead of glass resulted in a 50-fold increase
in percentage decomposition.
20
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Charles L. Thomas in his new book "Catalytic Processes and Proven Cata-
lyst" (23) discusses the ammonia decomposition reactions as follows -
1 This reaction may not ordinarily be thought of as a dehydrogenation
but it has all the characteristics. It is used to generate small
quantities of reducing gas, e.g., for metallurgical use. Catalysts of
the type used for steam reforming of natural gas, i.e., Ni on refractory
supports or iron oxide on similar supports, are used."
It would be ideal if means could be found whereby 95% or more of the
ammonia could be destroyed even before it left the oven. A British
Patent (<-4) claims the destruction of ammonia during the coking operation
by the addition of iron oxide in water suspension to the upper stratum of
coal in the coke oven. Up to 95% destruction of the ammonia is shown in
the data presented in the patent, which provides the strongest support
for this method of destruction which has been encountered.
(25)
Hill has reported some related studies in regard to ammonia decom-
position and coke ovens. It must be remembered that these investigations
were carried out with the aim of increasing ammonia yield. He reports
that Foxwell in 1922 found that iron (particularly in its metallic form
in coke oven walls and in coke) was very detrimental as was lime. This
effect of the surface material has previously been noted by White and
Melville (in 1905) , who found that fifty times as much decomposition
occurred on rough porcelain as on smooth glass; and by Woltereck (in 1908)
who observed that association started at 320°C in contact with metallic
iron cloth, and at 420°C on oxide of iron. Heckel (in 1913) had observed
the deleterious action of iron in practical oven tests. When coal to
which blast furnace dust had been added was coked, the yield of ammonia
decreased tremendously. Many other investigations were cited (19)
but the conclusions are the same.
'<
Wilson and Wells state that the temperature of formation of ammonia
is not the same for all coals. For some, ammonia formation begins at
temperatures as low as 300°C, but with others temperatures in the range
of 400 to 500°C are necessary. They add that in high-temperature coking,
"the major portion of the ammonia is probably formed at temperatures
above 600°C." Under favorable catalytic conditions this temperature
should be high enough to decompose ammonia. This argument could be used
to explain the ineffectiveness of attempts to decompose ammonia with flue
dust. The information on the effectiveness in destroying ammonia by the
addition of iron fines to the coal charge is contradictory.(12) Near
complete destruction (95%) was obtained when the top of the coal charge
in the oven was covered with a layer of iron oxide. However, the addition
of flue dust to the coal mixture for ferrocoke resulted in only partial
(20-40%) destruction of ammonia.
If complete destruction of ammonia can be achieved without affecting the
quality of the coke, there will be no need for any ammonia removal equip-
ment. This incentive justifies further experimental studv to see whether
essentially complete destruction in the oven is possible
21
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Coke-oven gas after tar removal could be passed through a catalyst bed
that would selectively decompose ammonia. The extent and rate of cata-
lytic cracking on iron oxide catalysts increase x*ith higher temperatures
and become significant above 500°C and at temperatures around 700°C the
dissociation is complete. At these temperatures, some of the higher
organics in the coke-oven gas would crack, but the major components from
the standpoint of heating value, methane and hydrogen would be stable.
Also, the remaining important by-product, benzene should be quite stable
at these temperatures, especially in the hydrogen-rich coke-oven gas
atmosphere. The less important by-products toluene, xylene and naphthalene,
would be progressively less stable at these high temperatures.
For the catalytic cracking of ammonia in the gas stream, four possibilities
have been considered: 1) a fluidized bed with iron as bed material,
2) a moving pebble bed reactor using pebbles of iron or iron oxide pellets,
3) a pebble bed reactor consisting of two stationary beds of pebbles that
are placed on stream and then regenerated periodically and 4) a thicker
brick furnace consisting of two units with one on stream while the other
is being regenerated by burning off deposits on the iron oxide bricks.
The fluid-bed system has the advantage of good gas-solids contact, accu-
rate temperature control, and simplicity in handling of the catalyst.
However, it suffers from higher pressure drop. The moving bed system is
much too cumbersome and expensive. The fixed pebble-bed unit has the
advantage of lower pressure drop and simplicity, particularly if the iron
catalyst has long life. The most promising system appears to be the one
involving parallel-fixed pebble units, using relatively cheap iron ore as
the catalyst. The catalyst would either be regenerated in place inter-
mittently by controlled oxidation with steam and air, or simply discharged.
To accurately determine cost factors experimental work is necessary to
study operating temperatures, gas velocity in bed, frequency of catalyst
fouling, effect on light oil recovery and effect on the volume and heating
value of the final coke-oven gas.
Ion Exchange for Ammonia.
Ammonia exists in solution predominantly as the ammonium (NH,)+ ion
unless the pH is higher than about 9.5. The ammonium ion is very similar
to the potassium ion in size and is precipitated by the same reagents
that precipitate potassium. Absorption of ammonium ion on ion exchange
resins is ordinarily very similar to the absorption,of potassium and
sodium ions. Therefore, conventional water softening ion exchange resins
whl.ch are selective for calcium and magnesium do a relatively poor job of
removing ammonium from dilute solutions. Total deionization by mixed bed
ion exchange resins will remove ammonium ions along with other cations
but this process is too costly for wastewater treatment.(27)
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Certain zeolites show unusual selectivity for the ammonium ion. A number
of these have been investigated by the Atomic Energy Commission because
they also show selectivity for cesium and potassium ions. A demonstra-
tion project at the Battelle Memorial Institute, Pacific Northwest
(Hanford Laboratories) showed that certain zeolites including the
naturally occurring mineral clinoptilolite had a high selectivity for
ammonium in natural and wastewaters.
The process employs the natural zeolite which is selective for ammonium
ions in the presence of sodium, magnesium and calcium ions. Regeneration
of the exhausted clinoptilolite is accomplished with solutions or
slurries containing lime. Lime provides hydroxyl ions which react with
ammonium ions to yield an alkaline aqueous solution. This ammonia solu-
tion is processed through an air stripping tower to remove the ammonia.
The problems of ammonia dispersion to the atmosphere are similar to
those encountered in direct air stripping of ammonia. The spent regenerant
is then fortified xtfith more lime and recycled to the zeolite bed to remove
more ammonia.
A cubic foot of granular clinoptilolite, regenerated with lime, was found
capable of removing ammonia from more than 2000 gallons of secondary
effluent. Ammonia removals exceeding 99 percent x^ere obtained for two
clinoptilolite columns in series during laboratory studies.(28)
In a private communication (29) with the Davison Chemical Division,
Baltimore, Maryland, it was stated that they manufactured several forms
of molecular sieves which are selective for ammonium ions when used as
ion exchangers. They further state that there is evidence that thermal
regeneration of these molecular sieves will produce nitrogen and water
in a catalytic decomposition rather than simply releasing ammonia. This
possibility should be investigated. Thermal regeneration occurs at about
550°C.
Air Stripping of Ammonia
Ammonia stripping is a modification of the aeration process used for the
removal of gases from water. Ammonium ions in wastewater exist in equi-
librium with ammonia and hydrogen ions as shown by:
NH + OH .. ^ -.NH.on
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Early studies of feasibility of stripping of ammonia from wastewater
(Kuhn, 1956) showed a major difficulty: the volume of air per unit
volume of water is very high, about 400 cubic feet per gallon of water
in a countercurrent-flow packed tower.(31) Ammonia solubility is higher
in cold water than in warm water, consequently, more air is required to
remove it. For example, at 0°C it would take about 800 cubic feet of air
per gallon of water to remove 90 percent of the ammonia.
There is also a question concerning the magnitude of the air pollution
problem created by the ammonia stripping of ammonia liquors. In a study
made at Mellon Institute O2) on stripping ammonia from hot excess liquors,
concentrations as high as 6000 mg NHg per cubic meter of air were obtained.
It is unlikely that this concentration of ammonia could be discharged to
the atmosphere.
Reverse Osmosis for Ammonia
Reverse Osmosis (33, 34) involves the forced passage of water through
membranes often cellulose acetate, against the natural osmotic pressure.
The wastewater must be subjected to pressures up to 750 psi to accomplish
separation of water and ions.
Proposed mechanisms for the action of the cellulose acetate membranes
used in reversed osmosis cells include sieving, surface tension, and
hydrogen bonding. Although plausible, the sieving theory does not
explain the action of the membrane in removing small ions. For example,
sodium and chloride ions, which are approximately the same size as water
molecules would easily pass through the membrane.
Problems associated with the application of the reverse osmosis process
include concentration polarization, membrane fouling, the passage of
certain ions through the membrane, and disposal of the concentrated
waste fraction. In a recent study of the use of this process for the
removal of nitrates from irrigation return water, it was found that a
portion of the nitrate ions passes through the membrane, thereby limiting
its usefulness in this application.
Chemical Oxidation or Reduction
The chemistry of aqueous nitrogen compounds is complex and the number of
possible oxidation or reduction reactions is great. Since nitrogen gas
represents an intermediate redox state for nitrogen and a much desired
end-product for nitrogenous removal, much effort has been devoted to
seeking applicable reactions. Most of these efforts have been specifically
aimed at the relatively low concentrations of nitrogenous materials
found in sanitary sewage but in principle the results apply to ammoniacal
liquors as well. Two sets of reactions are possible, oxidation of
ammonia or reduction of nitrate or nitrite to nitrogen gas. The best
known reaction for the production of gaseous products from the oxidation
24
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of ammonia is the breakpoint reaction with chlorine. This reaction
requires more than 8 mg/1 of chlorine for each mg/1 of ammonia oxidized.
The chlorination of ammoniacal liquors could utilize electrolytic
production of chlorine because of the inherent high chloride concentration.
Chemical reduction of nitrates in dilute solution has been proposed by
several investigators. Young, e£ ail, (35) proposed the use of powdered
iron as the reducing agent. Unfortunately, most of the nitrate is reduced
to ammonia under the conditions specified. Gunderloy, e_£ al, (36' made an
extensive study of denitrification by chemical means and came to the
conclusion that ferrous iron was the reductant of choice. Results in-
dicate, however, that only about half of the nitrate reduced is lost; the
remainder becomes ammonia. An excellent review of the oxidation and
reduction reactions between inorganic nitrogenous constituents has been
prepared by Chao and Kroontje.O/) In this review numerous potential path-
ways for the production of nitrogen gas from nitrogenous compounds are
given. The complexity of the possible reaction schemes makes theoretical
evaluation almost impossible and reliance on experimental information is a
must. A possible pathway is described which involves ferrous iron
reduction of oxidized forms of nitrogen. A laboratory evaluation of
this technique was attempted and results are summarized in the Appendix.
25
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SECTION V
BIOLOGICAL OXIDATION AND DENITRIFICATION
BIOLOGICAL OXIDATION OF COKE PLANT WASTES
The use of biological methods for the treatment of various waste waters
from coke plants has been practiced for many years, especially in Europe.
The earliest investigations were concerned with the treatability of
still wastes in conjunction with municipal wastes specifically for the
removal of phenolic compounds. According to Rudolfs, '3°.) ^g provides
an excellent summary on the biological treatment of coke plant wastes
to 1953, the initial efforts were made in the late 1800's. These early
experiments concluded that with municipal wastes, with dilution factors
of about 200, satisfactory removals of phenolics and thiocyanates were
possible. During the ensuing seventy years, numerous efforts, many
highly successful, have been made to treat a variety of ammoniacal
liquors, using both trickling filters and activated sludge, with and
without municipal sewage, and with and without dilution. Some of these
efforts that have particular historical interest or have direct bearing
on the design of the current experiment are outlined in the following
paragraphs.
The first extensive investigations were reported in 1907 by Frankland
and Silvester (39) who utilized bacterial contact beds and trickling
filters to satisfactorily treat a mixture of 9 percent ammonia still
waste in municipal sewage. A most interesting experiment was conducted
by Fowler and Holton (40) when they successfully treated ammonia liquor
using a trickling filter of crushed clinker. Essentially, this plant
consisted of a trickling filter with a recirculation ratio of nine to
one. This is the first reference to the treatment of ammonia liquor with-
out the use of an external diluent. Even though these and other
experiments were reported, Key (41) in 1935 concluded that when still
waste does not constitute"more than 0.5 percent of the influent of a
municipal sewage treatment plant, no adverse effects on treatment will
be noted.
The first reported recognition of the fact that ammonia liquors are
deficient in phosphorous is credited by Rudolfs to Nolte in Germany in
1939- Nolte proposed an activated sludge process supplemented by
available phosphates.
One of the very early efforts in the treatment of ammoniacal liquors in
this country is recorded in a patent assigned in 1922 to the Koppers
Company.(^2) xhis study, both laboratory and pilot scale, showed that
the phenolic content of properly diluted waste could be greatly reduced.
The first use of activated sludge in the United States for the treatment
of still wastes was by the Milwaukee (Wisconsin) Sewerage Commission
27
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(38)
according to Rudolfs . These experiments were conducted to determine
if still waste could be treated in a municipal treatment plant. The
results of this extensive investigation showed that phenolics were removed
as determined by taste test when the mixture treated consisted of 2 per-
cent still waste in municipal sewage. Additional experimental evidence
indicated that the phenolic wastes could be treated at considerably higher
concentrations and in some cases mixtures containing as high as 15 percent
were treated satisfactorily.
A series of detailed laboratory and field experiments were conducted by
the Chicago Sanitary District and reported by Mohlman (43» 44'. The treat-
ment criteria defined by these investigations included the limitation on
phenolics of 30 to 40 ppm in the mixture to be treated. The effect of
temperature on phenolic removal was also noted, removal being enhanced by
increased temperatures.
Two cooperative investigations between the Gary (Indiana) Sewerage Com-
mission and the United States Steel Company have been reported (45, 46)
on the disposal of still wastes in an activated sludge process. In the
earlier report with a minimum dilution factor of approximately 1 in 40
and an influent phenolics concentration of about 20 ppm, the plant effluent
contained only a few ppb of phenolics. The latter reference includes the
results of a new series of experiments conducted during 1966-67. During
this period, a maximum still waste flow of almost 400,000 gallons per day
was treated along with a flow of domestic sewage of about 40 mgd giving
a treatment concentration of only one percent ammonia liquor. The
approximate aeration time, as computed from data given in the paper, is
nine hours. The removal of phenolics was essentialljr complete. A major
obstacle to the discharge of ammonia liquor was the excessive chlorine
demand of the plant effluent. In the paper, this was attributed to the
more than 16,000 pounds of ammonia being contributed by the ammonia
liquor. The municipal waste alone contributes approximately 5,000 pounds
of ammonia. The conclusion that excessive ammonia concentrations were
responsible for this chlorine demand is questioned on the basis that
ammonia exerts a chlorine demand only when subjected to breakpoint chlo-
rination. The detailed chemistry of breakpoint chlorination is beyond
the scope of the present report but it can be shown that ammonia exerts
no demand until chlorinated beyond a one-to-one molar ratio. On a weight
basis this corresponds to a ratio of 5 chlorine to 1 ammonia-nitrogen.
Thus, the ammonia in the municipal waste alone would not exert a demand
until after over 60 mg/1 of Cl2 were added and with the combined waste,
over 250 mg/1 would be required. Since activated sludge plant effluents
generally are disinfected by chlorine dosages of less than 10 mg/1, no
chlorine demand resulting from ammonia would be expected either with or
without ammonia liquor. The more obvious explanation for the chlorine
demand and the resulting abandonment of the combined treatment program
is unremoved thiocyanate contributed by the ammonia liquor along possibly
with unreacted thiosulfate from the same source. No actual data on these
constituents is reported. Approximately 85 percent of the cyanide was
removed in the treatment plant.
28
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The combined treatment of ammoniacal liquors and municipal wastes is
practiced in the Chicago area. For example, Interlake Steel Corporation
discharges about 60,000 gallons per day of still waste plus some other
coke plant wastewaters and Wisconsin Steel Division of International
Harvester Company discharges about 100,000 gallons per day of undistilled
ammoniacal liquor plus other wastes to the Calumet System of the Metro-
politan Sanitary District. This apparently successful treatment system
operates at about a one percent liquor concentration. The East Chicago
activated sludge system accepts about 150,000 gallons per day of lime
distilled and dephenolized liquor from Inland Steel Corporation and
350,000 gallons per day of still waste from Youngstown Sheet and Tube
Company. The concentration of liquor in this instance is over 5 percent
but much of it has been dephenolized and lime distilled.
Several noteworthy attempts have been made to treat ammonia liquors
without dilution with domestic wastes. A United States Steel report (47)
outlines a series of experiments utilizing a large scale pilot-plant to
determine the treatability of still wastes containing various concentra-
tions of phenolics. The results indicate a strong influence of initial
phenolic concentration on the required period of aeration for obtaining
an effluent with less than one mg/1 of phenolics. To obtain this
effluent concentration required average aeration times of 9.4, 25, and
100 hours for initial phenolic concentrations of 10, 40, and 300 mg/1,
respectively. Wo mention is made of sludge concentrations involved in
the above tests but the results tend to indicate that they must have
been low.
In 1957, Bethlehem Steel Corporation (^8) began a pilot-plant study which
has evolved into a full-scale treatment facility for ammoniacal liquor.
The general conclusions drawn from the experimental phase of the project ^
were that phenolic loadings of 30 pounds per day per 100 cubic feet of
aeration capacity could be successfully treated with sludge concentrations
of 5700 mg/1 and a theoretical waste aeration time of 17.5 hours.
Loading rates of this magnitude were not recommended, however, because of
the difficulty in operating the system. At phenolic loading rates below
about 12 pounds per day per 100 cubic feet and at sludge ratios below
0.7 pounds of phenol per day per pound of sludge the system is reported
to operate smoothly. Probably the most controversial conclusion from
this work has been with reference to the limiting concentration for
ammonia in the system. Ammonia is reported to severly inhibit the
biological sludge at concentrations of 4000 mg/1 and the ammonia concen-
tration is considered the :'key design consideration for successful
oxidation of weak ammonia liquor." Among other important treatment
parameters,found were tar, temperature, nutritional requirements, and
pH. Recommendations included, limiting ammonia to 2000 mg/1 in the
biological reactor, removal of tar by storage of the liquor at ambient
temperature, maintenance of reactor temperatures of 80-95"F, addition of
phosphorus as phosphoric acid in a ratio of P to phenol of 1 to 70, and
keeping the pH of the effluent between 6 and 8. The full-scale plant,
29
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designed on these results was put on stream in September of 1962. This
plant consists of a storage tank, aeration tank, and clarifier, The
storage tank receives the weak ammonia liquor directly from the coke
plant and provides a detention time of approximately 9 days for equali-
zation and tar removal. The waste after leaving the storage tank but
prior to its introduction into the activated sludge aeration tank is
diluted with water for control of ammonia concentrations to less than
2000 mg/1, is dosed with phosphoric acid to provide necessary phosphorus,
and is steam heated. The aeration time, based on the undiluted discharge
of weak ammonia liquor, is about 56 hours. Sludge separated in the clarifier
is mostly returned to the aeration tank with excess sludge discharged to
the municipal sewerage system. The design capacity of this plant is more
than 4000 pounds of phenol per day; the average phenol load only 1300 pounds
per day. At this loading of less than one-third of design capacity, the
effluent phenol concentration, except during minor upsets, has remained
below 0.1 mg/1. The efficiency of removal of biochemical oxygen demand
(BOD-5),has been 85-95 percent. Removals of thiocyanate have ranged from
20 to 99 percent and averaged about 70 percent.
Several methods for improving the plant's capacity for thiocyanate
oxidation and cyanide removal have been pilot-plant tested by Bethlehem
Steel. These include the following: (1) a single-stage activated sludge
system in which the effects of many variables were studies, (2) two acti-
vated sludge systems in series, (3) a slag trickling filter in series
with an activated sludge system, and (4) a plastic-media trickling filter
in series with the full-scale plant. Reportedly, only the treatment on
the slag filter which oxidized up to 2.7 pounds per day of thiocyanate
per 100 cubic feet and removed 50 to 65 percent of the cyanide was
effective.
Just before the Bethlehem Steel Company's plant went on stream, Lone Star
Steel Company (49) ±n Texas began operating a full-scale activated sludge
plant on ammonia still waste liquor. The plant was designed to reduce
influent concentrations of phenols of 100 to 800 mg/1 to less than one
mg/1 for a waste flow of 50,000 gpd. The plant provides a pretreatment
storage pond, an aeration time of about 24 hours, a heating unit to
maintain temperatures above 70°F, a caustic feed pump to control p!l in
the range from 7 to 8, a phosphoric acid feeder, and provisions for sludge
recycle. From the pilot-plant tests conducted to determine design cri-
teria, it was established that treatment efficiency was not enhanced by
aeration chamber oxygen concentrations exceeding 0.5 mg/1. In actual
practice oxygen levels of 0.7 to 3.0 mg/1 have been iraintained and have
proven to be satisfactory. A loading factor of 0.2 to 0.25 pounds of
phenolics per day per pound of aerator suspended solids was found to give
optimum results. The best range for suspended solids in this plant is
2500 to 3500 mg/1. In actual plant operation, influent phenolic concen-
trations of 250 to 475 mg/1 and effluent concentrations of 0.1 to 0.3
mg/1 have been experienced with partial removal of cyanides.
30
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Dominion Foundries and Steel of Hamilton, Ontario, Canada have been
operating a biological treatment plant processing ammoniacal liquor since
1968. This plant, as described by Ludberg and Nicks, (50' provides for
tank storage of the x^aste for a period of about 2.5 days, prior to treat-
ment, dilution of the waste to 50 percent strength to control ammonia,
phosphoric acid addition, and aeration time based on undiluted waste of
37 hours, and a sludge recirculation rate equal to the flow of diluted
waste. The dilution rate is provided to reduce and maintain reactor
ammonia concentrations to less than 1200 mg/1. From average monthly
data given in the paper, the plant has processed diluted waste concentra-
tions of phenolics ranging from about 260 to 400 mg/1 with effluent
concentrations ranging from about 0.8 to 3.6 mg/1.
The removal of thiocyanate at the Dofasco plant has been erratic.
According to the report, the principal difficulty is that strains of
bacteria that most effectively oxidize thiocyanate function best at
a pH lower than is present in the aeration tank. The optimum pH for
these bacteria being about 7 with a range of 6.5-7.6. The actual aeration
tank averages about 8.3. A longer retention time is also stated to be
beneficial and a second set of aeration tanks operating in series with
the present ones is suggested.
In addition to these actual plant operations, two recent laboratory in-
vestigations are worthy of note. One of these studies was conducted by
the Koppers Company (51) to determine the treatment necessary to process
crude ammonia liquor, free leg ammonia liquor, and ammonia still waste.
The experiments were conducted in complete-mix activated sludge units
providing an aeration period of 24 hours for a waste diluted to 25 per-
cent for ammonia control. Results indicate that the three waste streams
vary in treatability and that differing design criteria are needed for
each .
International Hydronics Corporation has investigated the use of
several pretreatment steps for ammoniacal liquors to provide a more
easily treated waste. Essentially, the processes proposed remove sub-
stantial amounts of the ammonia and cyanides prior to biological
treatment by stripping, chemical precipitation, and coagulation. Process
claims include amenability to biological treatment without dilution. A
modified biological system called Bio-carb which is a mixture of acti-
vated sludge and activated carbon is also reported. This process pro-
duces an effluent low in carbonaceous materials and especially low in
odor and color as compared with other biological processes.
The scope of this literature review on the biological oxidation of am-
moniacal liquors has made no attempt to cover the vast numbers of
references on the subject. For example, very little of the research
and experience from either England or Germany has been included although
much of this work is reflected in the experiments and operating results
already described.
31
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However, discussion on the subject of the biological treatment of coke
plant wastes would be remiss without mention of the outstanding paper of
Ashmore, et al (52) in 1957. This laboratory study on the application
of the activated sludge process to the treatment of carbonization
effluents without sewage was conducted with special emphases on the role
of the sludge and the effect of effluent constituents on treatment.
In these experiments, utilizing completely mixed activated sludge
treatment units, the criterion for successful treatment was reduction of
the 4-hour permanganate value by 90 to 95 percent accompanied by con-
sistent removal of phenolics, thiocyanate, and thiosulfate to a few rag/1.
These studies were conducted on either free or lime distilled liquors.
Among many interesting observations reported were the results of studies
conducted to determine the limiting concentrations of various substances
that could be tolerated by an operating system. Among the important
limits found was one for chlorides. The conclusion reached was that am-
monium chloride concentrations as chloride below 2000 mg/1 had no effect
but that larger concentrations were increasingly detrimental. Data is
given which indicates that at ammonium chloride levels of 10,000 mg/1
as chloride no more than 1000 mg/1 of thiocyanate could be treated
effectively and that this figure fell to 500 mg/1 at a chloride concen-
tration of 20,000 mg/1. This latter chloride concentration corresponds
to about 8000 mg/1 of ammonia-nitrogen. However, it was shown conclu-
sively that the detrimental constituent was chloride rather than ammonia
by substitution of sodium chloride for the ammonium chloride in subse-
quent experiments.
In the presence of phenolics, the chloride effect was found to be more
important and for a given concentration of thiocyanate, the chloride
which could be tolerated in the aeration vessel and still permit total
thiocyanate removal, decreased with increasing phenol concentration.
For example, whereas an influent containing 1000 mg/1 of thiocyanate
could be treated in the presence of 10,000 mg/1 of chloride only 2500
mg/1 of chloride could be tolerated when 1100 mg/1 of phenolics were
present in the influent. This synergistic effect makes extrapolation
from one waste to another both difficult and uncertain.
Other interesting observations for the successful treatment of these
wastes include operation in the endogenous respiration phase to assure
high removals and levels of sludge wastage ranging to ten percent per
day. Recommended ranges of aerator pH were 6.7 to 7:3. Cyanide above
a concentration of about 40 mg/1 was found to be inhibitory and when
present along with sulfide was especially bad. The refractory organics
present after treatment appear to be a most important but poorly under-
stood parameter. This constituent is known to influence the dilution
necessary for efficient treatment, is associated with the effluent
color, and its detrimental effect is enhanced by heating and high pH.
This latter point along with the fact that calcium thiocyanate is at
about a factor of four more difficult to oxidize than ammonium thiocyanate
may make lime-distillation a poor pretreatment procedure.
32
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BIOLOGICAL NITRIFICATION AND DENITRIFICATION
No previous applications of the processes of nitrification and denitri-
fication have intentionally been made to remove nitrogenous constituents
from amtnoniacal liquors. The use of these processes has been proposed
to remove ammonia from municipal wastes and both are active mechanisms
in the transformations of nitrogen in nature. The basic research on the
two mechanisms has essentially all been conducted with regard to nitrogen
in soil and its affects on agriculture. Many excellent reviews on these..
processes in these areas are available and include those of Delwiche, (
Fry, (54) and Alexander.(55) xhe following paragraphs include a brief
summary of the pertinent information from these sources.
Nitrification is the biological process of converting ammonia to nitrite
and nitrate. In nature the two genera of bacteria responsible for these
changes are Hitrosomonas for ammonia to nitrite and Nitrobacter for
nitrite to nitrate. These organisms are strictly aerobic chemosynthetic
autotrophs. This means that these organisms utilize oxygen to oxidize
ammonia and nitrite to obtain energy to metabolize carbon dioxide into
cellular materials. These organisms are truly remarkable when it is
considered that they have the ability to synthesize from carbon dioxide,
bicarbonate, or carbonate the vast array of polysaccharides, structural
constituents, araino acids, vitamins, enzymes, etc., necessary for life.
The simplicity of their nutritional requirements is of course accompanied
by a tremendously complex metabolic system.
The capacity of these bacteria to utilize carbon dioxide or other inorganic
carbonaceous materials depends on their ability to obtain energy from the
oxidation of ammonia and nitrite for the purpose of reducing the inorganic
carbon to organic carbon. Chemically these reductions may be represented
as follows:
1) Ammonia oxidation (Nitrosomonas)
NH^ + + | 02»—. N02 ~ + H20 + 2H+ F = ea. - 60 kg. cal./mole
2) Nitrite oxidation (Nitrobacter)
N0_ + i 0 »- NO " F = ca. - 20 kg. cal./mole
3) Carbon dioxide reduction
•• CO + H9Q-^-CH,0 + 0. F = ca. - 120 kg. cal./mole
&L £* £* £*
Using these equations, the approximate free energies, and experimental
results on the amounts of carbon assimilated, the; efficiency of energy
transformation can be calculated. The ratios of carbon assimilated to
nitrogen oxidized by Nitrosomonas has been found to vary from approxi-
mately 14 to 70:1 and for Nitrobacter 76 to 135:1. The organism efficiency
33
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is then 3 to 14 percent. A major fallacy in these computations may be
the selection of water as the reducing agent in the conversion of carbon
dioxide with the production of oxygen. Although this reaction is the *
primary one in photosynthesis it may not be the major one in this parti-
cular chemosynthetic process. Thus, the efficiency of the systems are
questionable. However, the important parameter from a waste treatment
point of view is not the energy requirement but the overall stoichiometry
between the amounts of nitrogen oxidized to the amount of carbon reduced.
If the above ratios of nitrogen to carbon are assumed to hold in waste
treatment, then for every 1000 mg/1 of ammonia-nitrogen oxidized, about
20 and 70 mg/1 of organic carbon would be fixed. If this carbon is in
the average oxidation state of zero, then this quantity would have a
theoretical, chemical or biological oxygen demand of about 50 to 190 mg/1
as 02- Concurrently an oxidation resource of almost 3000 mg/1 as Q£ has
been formed as nitrate if subsequent denitrification to nitrogen gas is
assumed.
Some interesting consequences of this fundamental research that effect
the application of this process to waste treatment include bacterial
growth characteristics as characterized by kinetics, pH requirements, and
inhibitors. Early investigators found these organisms to be very slow
reproducers. Isolation of pure cultures of the nitrifiers is difficult
because this slow growth favors the more rapidly growing heterotrophs.
A very similar problem occurs in waste treatment.
Nitrifiers are favored by pH levels above 6 and many of the species prefer
a slightly alkaline medium. Since nitrification is accompanied by the
release of hydrogen ions, unless adequately buffered the process can become
self limiting due to a decrease in pH. These organisms are known to find
limestone beneficial and tend to coat the mineral. Both the necessary
buffering and the inorganic carbon requirement are satisfied by the
limestone.
Denitrification occurs when facultative heterotrophic organisms utilize
nitrate and nitrite as an oxygen substitute and produce nitrogen gas.
In the field of agriculture, denitrification leads to a loss of available
nitrogen which is disadvantageous; in waste treatment, the process is
most desirable. While only a limited number of organisms are capable of
oxidizing ammonia and nitrite, many are capable of reducing nitrite and
nitrate. Two distinct reduction reactions are possible. One of these
results in the formation of amino nitrogen which becomes a part of the
cellular synthesis of the bacteria. The other, true denitrification,
utilizes the two anions, nitrate and nitrite, as metabolic hydrogen
acceptors. This latter mechanism allows certain organisms to grow
anaerobically in media that would otherwise only support their growth in
the presence of oxygen.
The metabolic pathways for nitrate reduction are not definitely knox^n
and it appears that pathways may be different for differing organisms.
The major postulated reactions are given in Figure 2. The first step in
-------
reduction of nitrate involves its conversion to nitrite by an enzyme
nitratase. Some organisms are capable of this reduction step only but
others continue the reduction and many reaction pathways have been
postulated. Certain organisms are capable of almost quantitative con-
version of nitrite to ammonia, through the amino acid - protein route.
Of the total nitrogen being chemically reduced during intensive
denitrification as practiced in waste treatment, the fraction of nitrogen
reduced through this mechanism will be small. The major reduction
product of nitrite is hyponitrous acid. This compound is unstable and
can be further reduced to yield ammonia or nitrogen gas either directly
or through the intermediates nitrous oxide (^0) or hydroxylamine
(HH20U). The pathways leading to nitrogen gas are, of course, to be
favored for the denitrification of waste waters.
2NO,
+4e
2NH.
2W
-------
In addition to indicating the postulated reaction products for denitri-
fication, the figure shows the numbers of electrons, chemical ions, and
molecules involved in the reduction. The electrons shown are all utilized
in changing the nitrogen to a more reduced state. These electrons can
only be derived from a chemical oxidation.
In denitrification, this normally is some form of organic material, the
oxidation of which produces carbon dioxide. These organisms do not
depend on the availability of nitrate or nitrite but utilize these
materials only as a substitute for oxygen when it is unavailable. Thus,
in the presence of both oxygen and nitrate, most potential denitrifiers
grow aerobically with little or no effect on the nitrate; without oxygen
they grow anaerobically utilizing nitrate as their electron acceptor.
Most substances utilized for aerobic oxidation are utilized with equal
facility in media containing nitrate. There are denitrifiers capable of
utilizing sulfur, thiosulfate, and even hydrogen as replacements for
organic carbon as energy sources.
The second major point of note is that two moles of hydrogen ion are
utilized in the reduction of one mole of nitrate to nitrogen gas. Thus,
denitrification will tend to increase the pll whereas nitrification
lowered it. In denitrifying concentrated solutions, pH control may be
necessary.
The major environmental influences on denitrification in nature are the
type and amount of organic matter, oxygen concentration, acidity, and
temperature. The influences on nitrate demand are essentially the same
as those that affect the biochemical oxygen demand except for the oxygen
concentration. In denitrification the important oxidants are nitrate and
nitrite rather than oxygen as in BOD. In addition, the presence of oxygen
inhibits denitrification by supplanting a portion or all of the demand of
the organisms for a hydrogen acceptor.
The actual experience with nitrification and denitrification as a mechanism
for nitrogen removal from waste waters is entirely related to its use for
sanitary wastes. These wastes differ considerably from ammoniacal liquors
from coke plants in that they contain on an average about 20 tng/1 of
ammonia-nitrogen. Coke plant wastes may contain more than 250 times this
amount. Therefore, much care must be exercised in attempting to extra-
polate from one waste to another. However, much excellent experience has
been gained on this weaker waste and was the background for this phase
of the project. Among the many papers found to be helpful were those of
Ludzack and Ettinger, (56) Balakrishnan and Eckenfelder, (57, 58) Barth,
Downing, v"°' and Doxming and Hopwood. (61)
Downing was among the first to recognize and define some of the complex
factors involved in maintaining nitrification in a conventional activated
sludge system. The initial laboratory experiments with coke plant wastes
quickly indicated that nitrification would be most difficult to obtain in
36
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a single-stage activated sludge unit also responsible for oxidation of
the carbonaceous constituents. This difficulty results from several
factors. The nitrifying sludge population is difficult to maintain in
sufficient concentration in a single unit because of the necessity of
wasting large amounts of sludge resulting from the removal of large
amounts of organic contaminants. In addition, nitrification is knox^n
to be inhibited by high concentrations of organic materials and by
relatively low levels of heavy metals and cyanogens. The obvious choice
was to revert to separate carbonaceous and nitrification units in which
sludges and sludge-x^asting could be independently controlled. With the
addition of the also independent denitrification unit, the plant for
processing coke plant wastes for both carbonaceous and nitrogenous
removals becomes a three-stage biological treatment operation. Earth (59)
also has"recommended the use of the three-sludge system.
The first unit of three-sludge system is for the removal of the bulk
of the carbonaceous materials and is essentially the same as a normally
operated activated sludge system. It consists of an aeration compartment,
sedimentation compartment, capability for sludge recycle, and facilities
for wasting of sludge. The second or nitrification stage then receives
for its influent a waste low in carbonaceous matter and high in ammonia.
This system physically is similar to the first stage which allows inde-
pendent selection of operational variable to maximize nitrification
efficiency. The third step, denitrification, as a result of its anaer-
obic nature, is necessarily separate and consists of a mixed reactor
with reductant feed in addition to sedimentation and sludge recycle capa-
bilities.
The reducing agent utilized in the denitrification stage must be carefully
selected because it can have a large influence on both the ease or diffi-
culty with which the unit operates and on the cost of operation. Finsen
and Sampson (^2) present an excellent review of several possible reducing
agents and describe some of their experimental results. Among those
discussed are various sugars, alcohols, molasses, and the residual
reductants in treated sewage. The latter were not found to be in a form
suitable to act as a hydrogen donor (reducing agent) in the process.
Sucrose was tried at a ratio of 12 to 18 mg/1 per mg/1 of nitrate-nitrogen.
The use of sucrose was abandoned because the effluent was very turbid and
had a reminiscent of an alcoholic fermentation. Ethyl alcohol was also
tried. The alcohol was dosed at 523 parts per million with good results.
However, if it is assumed that the alcohol is oxidized to completion,
this concentration theoretically should have been capable of reducing
more than 380 parts per million of nitrate nitrogen. When decreases in
alcohol dosage rates were attempted, the unit's behavior became erratic.
Return of the unit to sucrose feed with careful adaptation proved that the
unit could utilize sugar efficiently. However, the expense of sucrose or
ethyl alcohol was considered prohibitive. A survey of alternative sources
of hydrogen donors indicated that corn sugar molasses might be satisfactory,
A major difficulty with molasses was found in the storage and dosing of
the material. Diluted molasses suitable for pumping quickly became con-
taminated with bacteria and fungi but addition of 10 percent sodium
37
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chloride to the diluted stock provided a solution to this problem. Among
the conclusions of Finsen and Sampson concerning the use of molasses were
that an excess of molasses amounting to about 20 mg/1 of chemical oxygen
demand was necessary to get essentially complete denitrification. The
ratio of molasses utilized as measured by COD as compared to nitrate
reduced was about 50 mg/1 of COD to about 15 mg/1 of nitrate-nitrogen.
38
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SECTION VI
DESCRIPTION OF PILOT PLANT
The pilot plant was designed to treat excess ammoniacal liquor at rates
up to 1 gpm. It was built in modular fashion as shown in Figure 3.
Three nearly identical modules were arranged in series so that each
successive module would receive treated waste water from the preceding
system. The first module was for oxidation of carbon compounds. The
second and third modules were for oxidation of ammonia to nitrate and
reduction of nitrate to nitrogen gas, respectively. Each of the modules
were designed as individual and independent treatment systems. Other
than the dependence of one module on another for a source of waste, the
operating variables of each unit were independent of the others. Because
of the toxicity of high concentrations of phenols, cyanides and other
compounds in coke plant waste, each of the treatment systems was designed
as a completely mixed activated sludge system. This design concept was
utilized because it is much less sensitive to high influent concentrations
and large variations in influent composition than other available systems.
Excess liquor from the coke plant tar decanters, flows by gravity to one
of two storage tanks prior to treatment. These tanks are provided to
reduce the liquor temperature from 150° F to 100° F or less, the optimum
range for biological activity. In addition to temperature reduction,
the storage tanks remove tar which escaped the decanters. It has been
previously reported that the residual tar content of excess ammoniacal
liquor inhibits biological activity. ^^ Each of the storage tanks
has a capacity of 1500 gallons or 24 hours at design capacity. The tanks
are operated on a fill and draw basis. Alternately, one tank is cooled
while the other is supplying waste for treatment.
The cool, tar-free liquor is pumped from the storage tank to the first
treatment module for aerobic oxidation of carbon compounds. The first
module consists of a completely mixed aeration tank and final clarifier.
Equipment details are listed in Table 3.
The aeration tank is a cylindrical steel tank with a detention time of
24 hours at 1 gpm. It is equipped with a 3 horsepower submerged turbine
mixer-aerator. Compressed air at up to 300 scfm is spurged under the
turbine to provide oxygen for biological growth. Temperature control
is provided by live steam injection. The original control system was
manual but after two occurrences of high temperature sterilization due
to excessive steam flox^ rates, the system was automated.
The effluent from the aeration tank flows by gravity to the center well
of the final clarifier for removal of biological solids. The clarifier
is a cylindrical steel tank with a cone bottom. It has an overflow of
200 gal./day/ft2, and an effective detention time of 150 minutes at 1
gpm. The clarifier is equipped with a scum baffle, a vee notch
39
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peripheral weir, and spiral sludge rakes. The settled solids are returned
to the aeration tank with a variable capacity pump. Recycle rates are
manually controlled between 0 and 1 gpm. The original system was designed
so that excess sludge could be wasted by periodically diverting the
recycle sludge to the sewer. This approach proved unsatisfactory and was
later replaced with a system of periodically draining a known percentage
of mixed liquor from the aeration tank to the sewer.
The effluent from the first module flows by gravity to a 55-gallon surge
tank. This partially treated waste is pumped from the surge tank to the
second treatment module for aerobic oxidation of ammonia to nitrate
(nitrification). The nitrification system consists of a completely mixed
aeration tank, a final clarifier, and a pH control system. Equipment
details are listed in Table 3.
The aerator-clarifier system in module two is identical to that described
for the first module with exception that a larger mixer-aerator (15
horsepower) was supplied to adequately handle the greater oxygen demand
anticipated in this system.
A pH control system consisting of a 55-gallon caustic storage tank and a
positive displacement metering pump was provided to maintain the pH between
7.0 and 8.5 in the nitrification system. Caustic is metered into the
aeration tank at a manually controlled rate to neutralize the nitric acid
produced by the oxidation of ammonia. Dry sodium carbonate is added in
batch quantities to the aeration tank to supply the nitrifying organisms
with inorganic carbon.
The effluent from the nitrification system flows to a 55-gallon surge
tank. The nitrified waste is pumped from the surge tank to the third
treatment module for anaerobic reduction of nitrate to nitrogen gas
(denitrification). The denitrification system consists of a completely
mixed anaerobic growth tank, a final clarifier, and an organic carbon
addition system. Equipment details are listed in Table 3.
The growth tank is a steam heated, cylindrical steel tank with a detention
time of 8 hours at 1 gpm. It is equipped with a 1/2 horsepower mixer to
maintain a completely mixed condition.
The final clarifier and sludge handling system is identical to the first
and second modules.
A system for the addition of organic carbon (molasses, methanol, or
sugar solutions) to the growth tank was provided. The system consists of
a 55-gallon mix tank with a 1/4 horsepower mixer, a 55-gallon pump tank
and a positive displacement metering pump. The organic carbon compound
is diluted and mixed with water in the mix tank. This solution is trans-
ferred to the pump tank by gravity and metered at a manually controlled
rate to the growth tank.
40
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lOTOMETEK.
•ORJaANlC CARBON
5TOKA&E
EXCESS
AMMON1ACAL LiaUOR
STORAGE TANKS
FIGURE 3
PILOT PLANT
FLOW'UTAGRAM
-------
TABLE 3: PILOT PLANT EQUIPMENT
Equipment
Storage Tanks
Module I
Waste Feed
Dilution Water
Aeration Tank
Mixer-Aerator
Clarifier
Sludge Recycle
Module II
Waste Feed
Dilution Water
Aeration Tank
Mixer-Aerator
Clarifier
Sludge Recycle
Feed Rate
Size
Volume
0
0
1 gpm
1 gpm
0-1 gpm
0
0
0
6 ft. dia. x 8 ft. SWD 2000 gal.
1/4 hp
5 ft. dia. x 12 ft. SWD 1500 gal.
3 hp v -
3 ft. dia. x 3 ft. SWD 150 gal.
1/4 hp
1/4 hp
Caustic Addition Pump 5 -
1 gpm
1 gpm - . -
5 ft. dia. x 12 ft. SWD 1500 gal.
15 hp
3 ft. dia. x 3 ft. SWD 150 gal.
1 gpm 1/4 hp
1750 ml./min. 1/6 hp
Module III
Waste Feed
Dilution Water
Growth Tank
Mixer
Clarifier
Sludge Recycle
Organic Carbon
Addition Pump
0
0
0
5
1 gpm
1 gpm
1/4 hp
4 ft. dia. x 6 ft. SWD 500 gal.
1/3 hp
3 ft. dia. x 3 ft. SWD 150 gal.
1 gpm 1/4 hp
1750 ml./min. 1/6 hp
42
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Each of the three modules is provided with independent control of waste
volumes and concentrations. Volume control is provided by 0 to 1 gpm
variable capacity pumps supplying waste to each system. Dilution water
for adjustment of waste concentration is also supplied to each system.
Dilution water rates of 0 to 1 gpm can be metered into any of the mix
tanks by a manually adjusted flow control system. The control system
consists of a rotometer and a flow control needle valve. The use of
these two control systems allows variations to influent flow from zero
to maximum design capacity and simultaneous variations in influent
concentration from zero to full waste strength.
Coke plant waste water is deficient in phosphorus and will not support
biological activity without phosphorus addition.^48> 50' 63> 64^ A
system was installed to continuously feed phosphoric acid to the first
module aeration tank. The system consisted of a 5-gallon drip pot with
a discharge needle value for the continuous feed of 75% phosphoric acid.
From pilot plant start up, this system was plagued x
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SECTION VII
SAMPLING AND ANALYSIS
The sampling and analysis program conducted during the pilot plant study
x*as designed to provide: (1) data required for routine plant operation
and control; and (2) detailed data on vzaste loading, material balance
and process efficiency. This information was obtained from analysis of
samples taken from twelve sample points as shown in Figure 4. Samples
from each of these points were collected regularly by the plant operator.
Those analyses and measurements required for routine operation x^ere per-
formed by the operator in the pilot plant laboratory. Those analyses
which established plant performance and efficiency but were not required
for routine operation were analyzed in a remote analytical laboratory.
The sampling and analysis schedule used throughout the study is shown in
Table 4.
Analyses and measurements performed by the operator for routine control
of the pilot plant included flow rates, temperature, dissolved oxygen,
settleable solids, alkalinity, pH, and dissolved solids. For convenience
arid simplicity the biological solids level was determined indirectly by
the measurement of settleable solids. Periodic analysis of suspended
solids were used to correlate settleable solids data with the more con-
ventional mixed liquor suspended solids.
In addition to the measurements and analyses performed as a part of normal
plant operation, a supplemental analytical program was conducted at a
remote laboratory. This program was designed to determine waste loadings,
material balances and treatment efficiencies. Samples collected at the
pilot plant were preserved by refrigeration during storage and shipment.
Generally, the analytical work was in progress within four hours of sample
collection. All analyses were performed in accordance with the recom-
mendations of the 12th edition of Standard Methods for theExamination
o f Jffater and Was te Water.
The first treatment module was designed for removal of organic carbon
and cyanide compounds. Total organic carbon and cyanide were selected,
therefore, as indicators of waste loading, and treatment efficiency.
Influent and effluent analyses for the indicator materials were performed
three days each week. Difficulties with obtaining reproducible total
organic carbon results during the initial part of the study resulted in
the conversion from this analysis to chemical oxygen demand (C.O.D.).
In addition to the indicator materials, regular analysis (weekly or more
frequently) for phenolics, thiocyanate, sulfide, ammonia, and organic
nitrogen were performed so that loadings and treatment efficiencies for
these materials could be determined.
45
-------
EXCESS AMMONIACAL LIQUOR
T-N-
STORAGE
TANK
out
>0
j-CXh
STORAGE
TANK
DILUTION WATER Q
J
F.C.V. FLOW CONTROL VALVE
F.I. FLOW INDICATOR
SAMPLING POINTS
ORGANIC CARBON
MIX TANK
DILUTION WATER
CAUSTIC
DILUTION WATER
,,£
F.C.V.X
H3P04 DRIP POT
AERATOR
*'«
dy?
CLARIF.
*l
•^ixh
FCV\/
«i N/
[F.C.V.
]F.I.
AIR
(5)
OVERFLOW
TO SEWER
IF. i.
F.CV.
ORGANIC
CARBON
STORAGE
DILUTION WATER
4,,.
XFC.V.
AERATOR
#2
dt®
CLARIF.
:CV\y
Kh N/^
F.C.V.
«-H*h
JF.C.V.
]F.I.
AIR
11
n
OVERFLOW
TO SEWER
AERATOR
•3a
ci@
CLARIF. |
*3
^c.v. \
>*1 N
FC.V.
•*-H>4i
<
UJ
-------
TABLE 4
SAMPLING AND ANALYSIS SCHEDULE
Parameters
Flow
Temperature
Seechi Disc or Equivalent
pH
Conductivity
Alkalinity
Dissolved Oxygen
Suspended Solids
Settable Solids
Total Organic Carbon
COD
BOD-5
Phenolics
Cyanides
Thiocyanates
Sulfides
Ammonia
Organic Nitrogen
Nitrite
Nitrate
Phosphate
1
D A W P
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
2
DAW
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Sampling Location
3
4 ^5
Sampling Interval"""
DAW
X
X
X
X
X
X
X
X
X
X
D A W P
X
X
X
X
X
X
X
X
X
X
X
X
X
D
X
1
6
D
X
.
!
7
D
X
8
D
X
-•>
9
D
X
A
A P
X
X
X
!
B
A , P
X
X
X
c
A P
X
X
X
1. D - Daily
A - Alternate Days (Hon., Wed., Fri.)
W - Weekly
P - Periodically
-------
The second treatment module was designed for oxidation of ammonia to
nitrate and nitrite followed by the reduction of these compounds in the
third module to nitrogen gas. As an indication of waste loading and
treatment efficiency influent and effluent samples from both modules
were analyzed three times each week for ammonia, nitrate, and nitrite.
To provide a more complete nitrogen balance across the system, organic
nitrogen was also determined routinely.
48
-------
SECTION VIII
OPERATIONS AND RESULTS
The operation for almost one year of the three-stage pilot plant resulted
in the collection of much detailed data. The experiment by its very
design was unsteady and when combined with variations in waste character-
istics and operating difficulties make data interpretations difficult
and somewhat uncertain. However, in this section an attempt will be
made to present the chronology of operations, the data from the three
operational treatment stages (carbonaceous removal, nitrification, and
denitrification) and to discuss the results obtained in relationship to
operating conditions. Because of the many variables and the dependency
of the succeeding operating units on previous treatment operations, this
section will present the data and discussion of each unit in the sequence
in which they were operated.
Most of the discussion in this section will be based on summarized data
to be found within this section. More complete analytical data sets are
provided in the appendixes to this report. Summarized or averaged data
is used because it reduces both the variability of the data and because
it reduces to manageable dimensions the problem of presenting and inter-
preting the results. Two methods of selecting averaging periods were
used for the data. During the early portion of the test, averaging
periods were chose to represent periods in which a single batch of
waste was used as the plant influent. This period was characterized by
use of high dilution rates which allowed the use of a uniform influent
(one filling of a storage tank) for periods of several days. This per-
mitted the averaging of several determinations for most variables. As
dilution rates decreased, the time required to empty a waste storage
tank decreased to little more than one day. During these intervals an
arbitrary averaging period of about one week was selected.
In the tables to follow, the averaging period for the successive stages
of operation have been selected so as to represent as closely as possible
a slug of waste passing through the treatment complex. In other words,
as a first approximation, the averaging periods have been selected to
represent periods corresponding to the delay based on detention times.
Thus, the averaging period for the nitrification and denitrification
unit lag by one and two days, respectively, the period selected for the
carbonaceous unit because of the 24-hour detention times used in both
the first and second treatment units. The numbers used for designating
the operational periods in the tables of this section are days of
operation counting from 1 February 1970.
49
-------
THE EXCESS AMMONIACAL LIQUOR
Before proceeding with a discussion of each of the sequential treatment
units, a description of the character of waste itself through the
experiment is necessary. Waste strength and variability are most
important parameters in the operation of biological treatment systems.
The characteristics of the waste for the averaging periods are given in
Table 5 and a summary for the major characteristics of the waste are
given in Table 6. (Detailed data is included in Appendix A-l.) These
results show the waste to be highly variable in chemical oxygen demand,
phenolics, thiocyanate, sulfides, and organic nitrogen, but less so in
ammonia. Actually of more importance to waste treatment than simply
the variability of waste strength is the rate of change in the concen-
trations of the constituents. From Table 5, it is apparent that changes
from one averaging period to another can exceed a factor of 2 for COD
and approach this factor for phenolics, thiocyanate, and ammonia. These
variations must be dampened prior to entry into a biological plant if
overloads and underloads are to be avoided.
An important criterion for the operation of biological systems treating
excess ammoniacal liquor is the percentage of liquor being treated.
Influent dilution factor is one of the major controls the operator has
on the system. Two approaches are available for estimating the actual
dilution rate used at a specific time. First, the operator attempted
to establish a specified dilution rate by pump adjustments and monitored
the flow rates for both the liquor and dilution water (given in Appendix
B-l). However, because of variations in flows, a better estimate of
actual dilution rates was possible through the use of a materials balance
computation for conductivity. Conductivity was chosen because it is a
conservative constituent, that is, the concentration is not affected
significantly by the treatment. In addition, the large difference between
the conductivities of the waste and the dilution water makes the computa-
tion more reliable. Since conductivity is a measure of dissolved solids,
the conductivity in and out of the treatment system is hypothesized to
be equal. This may be written as
VD + VL = % + VCE
where
QD = quantity of dilution water,
QT = quantity of liquor,
LI
C = conductivity of dilution water,
C - conductivity of liquor, and
LI
CE = conductivity of the effluent,
50
-------
TABLE 5 - EXCESS AMMONIACAL LIQUOR
PERIOD
1-5 2/1-5
6-13 2/6-13
14-21 2/14-21
22-29 2/22-3/1
30-39 3/2-11
40-43 3/12-15
44-48 3/16-20
49-55 3/21-27
56-57 3/23-29
53-60 3/31-4/1
61-67 4/2-8
63-73 4/9-14
74-76 4/15-17
77-81 4/18-22
82-84 4/23-25
85-88 4/26-29
89-91 4/30-5/2
92-95 5/3-6
96-98 5/7-9 •
99-103 5/10-14
104-108 5/15-19
109-112 5/20-23
113-116 5/24-27
117-121 5/28-6/1
122-129 6/2-9
130-136 6/10-16
137-143 6/17-23
144-150 6/24-30
151-157 7/1-7
158-164 7/3-14
165-171 7/15-21
172-173 7/22-28
179-135 7/21-8/4
186-192 3/5-1 1
193-199 8/12-18
200-206 3/19-25
207-213 3/26-9/1
214-220 9/2-3
221-227 1/9-15
228-234 9/16-22
235-241 °/23-29
242-248 9/30-10/6
249-255 10/7-13
256-262 10/14-20
263-269 10/21-27
270-276 10/28-11/3
277-281 11/4-10
234-290 11/11-17
291-297 11/18-24
298-104 11/25-12/1
105-311 12/2-',
112-318 12/9-15
119-125 12/16-22
176-332 12/23-21
313- Til 12/30-1/1
') '.0-346 1/6-12
!•'' 7-152 1/13-18
5.
8.5
8.7
3.9
8.7
8.8
8.7
8.4
8.7
9.1
8.9
8.8
8.6
8.5
8.4
8.5
8.4
8.4
8.5
8.6
8.6
8.6
8.5
8.6
3.6
8.6
8.6
8.6
8.5
3.4
8.4
8.3
8.4
8.4
8.5
3.6
8.5
3.6
8.6
8.6
8.6
8.6
8.6
8.6
3.7
8.7
8.6
8.6
8.7
3.6
8.4
3.5
8.7
S.6
8.6
8.7
8. 7
8.7
ALKALINITY
mg/1
CaC03
1330
1630
2540
1760
1870
1520
1220
•1600
27 00
2630
2170
1810
1730
1680
1560
1360
1340
1420
2100
1440
1660
1750
1730
1820
2000
1590
1440
1630
1300
1330
1230
1400
1450
1430
1500
1690
1650
1830
2290
2230
2290
2610
2410
2190
2120
1630
1840
1890
1330
1540
1490
2370
1970
I '100
2190
2240
2190
CONDUCTIVITY
jumhos
15400
14100
10900
12800
12200
13900
14250
16700
13300
14200
12500
12100
21000
24450
26400
23400
23900
21200
20000
20400
23400
20700
21000
18900
20700
24200
29400
24600
25800
26200
26500
24700
22700
19600
20000
21300
15000
21500
28500
28500
22300
26500
28000
27500
29300
26300
29200
27400
26300
23200
27600
29900
31800
30700
21700
1120')
29300
ORGANIC
CARBON
mg/1 C
700
720
760
760
730
1370
1450
1480
1140
1700
2360
2030
2970
3700
2660
1990
1920
1260
1670
1650
1510
1600
930
1070
1700
1200
510
460
720
1290
880
a ---
Sic?
3630
3400
2920
3460
3360
3170
2900
2830
2460
2700
2930
3260
3350
7670
9230
9010
9120
10400
9600
9720
3180
5420
3660
5770
5130
5740
3660
6600
5710
6520
6750
5330
5330
m ~*
!»«?
2330
1710
1830
6170
5790
.
2460
4160
4030
PHENOLICS
mg/1
PHENOL
500
410
500
525
530
780
765
645
930
730
1330
850
560
665
850
830
700
900
650
650
580
490
540
-
420
500
550
710
1240
1700
1860
1900
2150
2380
650
950
920
1070
1 080
11 10
1120
1430
1130
I 100
1290
13!')
101"
1200
CYANIDE
mg/1
CN
10
23
32
27
22
17
10
15
37
16
21
28
25
26
21
21
24
28
30
32
35
24
36
30
36
30
23
25
28
27
27
26
26
23
25
21
27
13
14
11
18
22
19
10
18
25
35
20
18
20
13
32
26
23
1 7
22
23
THIOCYANATE
mg/1
SCN
250
210
190
250
250
240
290
175
240
390
550
400
360
230
100
410
360
290
370
350
300
310
-
300
320
290
430
140
530
770
1540
630
1100
660
480
540
640
•540
560
1)0
690
650
640
650
670
610
650
SULFIDES
n.g/1
S
0
7
50
22
4
0
0
23
2
2
0
2
3
3
6
0
0
0
0
0
0
0
-
2
0
4
2
2
1
1
1
2
2
4
0
1
•)
3
1
0
1
4
1
4
1
•)
2
AMMONIA
mg/1
N
1860
1910
1800
1920
1900
1960
1890
1780
2250
2010
1960
1880
3110
3570
4170
3500
3740
3200
3490
3350
3630
3400
3400
1100
3400
3850
3880
3740
3620
3620
3530
3270
3170
2720
2840
3040
2200
1030
4180
4120
1150
4020
1960
3780
4200
3630
4070
3750
3610
1S50
1810
-',190
4290
2490
202')
2040
1790
S§z
3Sk
ss«
ggt
100
115
90
90
100
90
100
70
250
200
120
200
190
225
15
375
180
180
180
150
260
100
110
120
140
140
150
230
200
170
190
260
-
230
200
200
90
140
170
260
180
250
700
2300
2 1 00
80
TOTAL
NITROGEN
mg/1 N
1970
2040
1910
2000
2070
1990
1890
—
2040
—
—
3830
3710
—
3340
—
3570
__
3600
3640
—
3440
4240
4070
3930
3820
3780
3800
—
3280
284fl
2970
3190
2350'
3190
4420
4330
3530
4220
4210
—
4440
3840
4290
1850
3760
4030
4080
4390
4550
1200
4330
4150
3880
51
-------
Since the only contributors of solids and liquids to the system are the
dilution water and the liquor and neglecting any losses in the blowdown,
this equation can easily be reduced to give for the fraction of liquor
being treated,
Q
(2)
D
The solution of this equation requires the knowledge of the conductivities
of the dilution water, liquor, and effluent for each averaging period.
^ • A 1
Values of the conductivities for the liquor are given in Appendix A-l
and for the effluent from the carbonaceous unit in Appendix A-2. The
conductivity of the dilution water was by comparison low and was relatively
constant throughout the test. A constant value of 600 micromhos per cm.
has been assumed for the conductivity of the dilution water.
TABLE 6; SUMMARY OF CHARACTERISTICS - EXCESS AMHONIACAL LIQUOR
Parameter Mean Median
pH 8.6
Alkalinity 1800 1700
mg/1 CaCO.
Conductivity 23000 23000
umhos/cm2
COD 5800 5700
mg/1 02
Phenolics 950 850
mg/1 Phenol
Cyanide 24 23
mg/1 CN
Thiocyanate 470 380
mg/1 SCN
Sulfides 3.7 2
mg/1 S
Ammonia 3200 3400
mg/1 N
Organic N 270 180
mg/1 N
Standard Deviation
390
5800
2500
460
260
8.2
800
430
Range
8.3-9.1
1200-2700
11000-32000
2500-10000
410-2400
10-37
100-1500
0-50
1800-4300
15-2300
52
-------
CARBONACEOUS TREATMENT UNIT
The carbon removal unit began operation on 8 January 1970 when an influent
flow of one (1) gallon per minute of a 15 percent dilution of excess
ammoniacal liquor was initiated. This flow rate represented an aeration
time of approximately 24 hours. Phosphoric acid was added according to
the schedule given in Section VI. The system was seeded on 8 January
with unknown quantities of three different materials, Bethlehem Steel
biological solids, soil from in and around the Houston Coke Plant by-
products area, and final clarifier sludge from the Houston Works trickling
filter sewage plant. Unfortunately, the system was pasteurized on
15 January by the accidental increase in aeration tank temperature above
150° F. The system was restarted on 16 January and seeded with the same
materials previously used.
The remainder of the month of January was basically used for adapting
organisms to the waste, accumulating organisms, and learning to operate
the unit. During this period recycle flow was one (1) gallon per minute
and no sludge was intentionally wasted. On 1 February collection of
operating and analytical data was begun.
Table 7 summarizes the operating information for the individual averaging
periods for the carbonaceous unit. More detailed information can be
found in Appendix B-l. Table 8 gives the chemical composition of the
influent to the unit and Table 9 gives the effluent quality, percent
removals, and loadings. These three tables provide a summary of the
chronology of operation, the data obtained, and the problems encountered.
The results of the computation for percentage of waste in the influent
are given in both Tables 7 and 8. The original project plan called for
increasing waste percentages in a consistent manner. However, because
of unit upsets which will be discussed later, several reductions in
liquor percentages were found to be necessary in order to maintain adequate
treatment levels. A plot of the percent waste treated in the carbonaceous
unit for the duration of the test is given in Figure 5.
In addition to the waste concentration being treated, Table 7 provides
data on several other operational parameters. Among items of major
interest are reactor temperature, pH, dissolved oxygen, and suspended
solids. Also included are measures of the clarity of the effluent (Seechi
disk), blowdown rate, chemical additives used and special operational
condi tions en counte red.
53
-------
TABLE 7; OPERATING CONDITIONS. CARBON REMOVAL UNIT
PERIOD
i
1-5
6-13
14-21
22-29
30-39
40-43
44-48
49-55
56-57
58-60
61-67
68-73
74-76
77-81
62-84
85-88
89-91
92-95
96-98
99-103
104-108
109-112
113-116
117-121
122-129
1 30- 1 16
137-143
144-150
151-157
158-164
165-171
172-178
179-165
166-192
193-199
200-206
207-211
214-220
221-227
228-234
2I5-2M
2V2-248
2-.9-25S
256-262
263-269
270-276
277-283
284-290
291-297
298-104
105-311
312-318
319-325
326-132
111-319
340-346
147-152
B
fi'l
INFU'E
PERCENT
13
15
17
15
15
16
16
15
22
29
23
27
25
14
16
42
38
47
61
64
57
70
76
73
82
89
56
65
60
54
49
72
78
74
74
74
86
71
68
79
81
75
40
17
2)
41
47
58
10
22
15
45
45
58
49
46
57
b.
a"
TEMPERATI
80
76
79
80
82
77
80
78
80
81
82
80
8!
82
85
85
79
76
79
86
83
85
86
86
84
90
89
89
88
89
88
87
90
91
88
89
85
89
90
90
84
78
76
75
82
72
72
70
7)
77
89
90
86
88
89
91
86
x
a.
8.3
8.1
8.0
8.2
7.8
6.6
6.4
7.5
7.5
7.0
7.8
8.5
8.3
8.1
8.1
8.1
7.8
7.6
8.3
8.3
8.2
8.2
8.2
8.3
8.3
8.3
8.2
8.1
8.0
8.0
6.0
8.1
7.9
8.1
8.2
8.2
8.0
7.9
7.9
7.8
7.9
8.0
8.0
8.1
8.0
8.1
8.2
8.2
8.2
8.1
8.1
8.2
8.2
8.1
8.3
8.2
8.2
(v
a
DISSOLVED
OXYGEN, me
2.7
3.7
4.1
2.8
2.3
2.0
1.
2.
2.
2.
I.
1.
1.
1.
1.0
1.9
1.2
1.0
1.1
0.8
2.7
2.3
2.8
3.0
2.3
2.3
2.6
2.5
1.0
2.4
2.0
2.0
2.0
2.2
o
g
s»
REACTOR SI':
SOLIDS , 1
1420
1220
700
250
100
140
850
tolioff
Cone
«1/1
K
a o
sg
X >J
0
5
10
19
36
73
49
70
62
41
34
34
36
190
180
200
170
160
210
280
210
180
180
130
80
45
50
39
53
57
84
160
120
140
70
140
170
160
140
40
8
8
2
4
15
12
3
1
4
65
190
180
220
280
260
260
RETURN
SLUDGE
3
18
21
40
63
140
100
170
140
61
49
94
340
740
400
400
290
600
610
700
540
380
360
240
125
90
100
78
108
79
180
210
240
220
210
210
310
280
190
30
8
8
2
1
16
16
6
5
5
90
330
360
400
450
430
560
,
X
U*
SECCHI D:
INCHES
8
7
8
11
9
9
6
6
5
5
4
5
3
4
4
3
3
3
4
4
3
4
4
2
2
2
3
3
3
3
1
4
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
3
4
4
3
3
3
3
2
1
BLOUDOWN,
PERCJNT/DA1
2
2
'i
2
2-6
4-6
4
2-6
2
2
2
2
2
2
2
2
2
2
2
2
2
2-6
2-6
2
2
2
2
2
2
2
2
2
0
0.5
1
1
0.5
0.5
Chemical Additives per Period
mi.
OSPHORIC
ACID
£
e
41
E
i
u
41
f
ui
750
750
1500
1300
2900
2800
2200
1500
2200
2200
2200
3000
1500
2200
15OD
1500
2200
2200
2200
2200
1500
JCOO
750
750
1500
2200
1500
750
15QO
750
750
2200
1500
1500
1500
1500
RIBUTYL
HOSPHATE
H 0.
30
50
100
125
125
150
250
225
570
450
100
300
300
300
500
300
500
300
300
300
400
500
600
400
800
100
100
300
500
300
ISO
300
150
150
400
300
200
200
300
pounds
IMESTONE
^
3
li
ta _i
is
£
2
in
ODIUM
ARBONATE
w u
I
2
4
5
2
Special Conditions
5
K
^_
X
X
X
X
x
x
x
)(
x
x
X
X
x
X
X
X
x
X
X
z
*
x
X
X
X
x
x
X
x
x
x
X
x
y
X
X
z
1
SSOLVED 0X1
S
X
X
X
X
X
S
TEMPERATU
X
X
X
X
|
X
X
X
X
X
x
x
x
X
x
x
X
X
X
x
x
X
x
X
x
X
X
X
X
a
3
V)
%.
X
x
COMMENTS
3 mi per 4 gals, undiluted
waste, phosphoric acid.
(64) Temp.- 123'F.
0.0. not available.
(136) D. 0. - 0.2 mg/1.
(173) D.O. = 0.1 mg/1.
(199) D.O. • 0.5 mg/1.
D. 0. marginal.
(223) D.O. - 0.3 mg/1.
D. 0. marginal
System reseeded.
(278) Temp.- 64°F.
(289) Temp." 61'F.
(297) Tenp.- 62°F.
Heating reactor.
54
-------
TABLE 8: INFLUENT. CARBON REMOVAL UNIT
PERIOD
1970-71
1-5 2/1-5
6-13 2/6-13
14-21 2/14-21
22-29 2/22-3/1
30-39 3/2-11
40-43 3/12-15
44-48 3/16-20
49-55 3/21-27
56-57 3'28-29
58-60 3/30-4/1
61-67 4'2-8
68-73 4/9-14
74-76 4/15-17
77-81 4/18-22
82-84 4/23-25
35-88 4/26-29
89-91 4/30-5/2
92-95 5/3-6
96-98 5/7-9
99-103 5/10-14
104-108 5/15-19
109-112 5/20-23
113-116 5/24-27
117-121 5/28-6/1
122-129 6/2-9
130-136 6/10-16
137-143 6/17-23
144-150 6/24-30
151-157 7/1-7
158-164 7/8-14
165-171 7/15-21
172-178 7/22-28
179-185 7/29-8/4
186-192 8/5-11
193-199 8/12-18
200-206 8/19-25
207-213 8/26-9/1
214-220 9/2-8
221-227 9/9-15
228-234 9/16-22
235-241 9/23-29
242-248 9/30-10/6
249-255 10/7-13
256-262 10/14-20
263-269 10/21-27
270-276 10/28-11/3
277-283 11/4-10
284-290 11/11-17
291-297 11/18-24
298-304 11/25-12/1
305-311 12/2-8
312-318 12/9-15
319-325 12/16-22
326-332 12/23-29
333-339 12/30-1/5
340-346 1/6-12
347-352 1/13-18
PERCENT
WASTE
13
15
17
15
15
16
16
15
22
29
23
27
25
34
36
42
38
47
61
64
57
70
76
73
82
89
56
65
60
54
49
72
78
74
74
74
86
71'
68
79
81
75
40
17
23
43'
47
58
30
22
35
45
45
58
49
46
47
ORGANIC
CARBON,
mg/1 C
90
110
130
115
110
220
230
220
250
500
550
550
740
1260
950
840
730
590
1020
1050
860
1120
710
780
1390
1070
290 (?)
300(?)
430
1000
650
f-t
8 to
580
1600
1640
2250
2000
1710
1420
2040
1920
2000
2170
2400
2880
5500
6300
7100
7400
7800
3800
1650
1900
2320
4100
3350
1550
1260
3030
3000
2570
3800
3300
2680
2740
I-
370
800
1100
4200
4300
1050
1460
1980
PHENOLICS
mg/1
PHENOL
66
.60
85
80
80
120
120
100
210
200
450
350
260
430
590
480
570
800
360
420
350
260
260
-
330
370
410
530
1100
1200
1260
1500
1750
1800
260
-
220
400
500
630
330
250
520
520
500
750
640
470
560
CYANIDE
ng/1
CN
1.3
3.5
5.5
4.1
3.4
2.7
1.6
2.2
8.1
4.6
4.9
7.7
6.4
8.9'
7.7
8.8
9.1
13.4
18.3
20.4
20.0
16.8
27.4
21.9
29.6
26.7
12.9
16.2
17
15
13
19
20
17
18
16
19
9
9
15
15
16
8
2
4
10
16
12
5
4
6
14
12
13
8
10
12
' THIOCYANATE
mg/1
SON
33
32
32
37
40
38
43
40
65
130
230
190
230
160
75
340
320
160
240
210
160
150
230
240
210
320
120
380
520
1200
510
820
260
110
230
300
310
170
80
240
290
290
380
330
280
310
<:
M _i
|f«
240
290
310
290
280
310
300
270
500
580
450
510
780
1210
1500
1470
1420
1500
2130
2140
2070
2330
2580
2260
2780
3420
2180
2440
2170
1960
1730
2360
2480
2020
2100
2300 .
1900
2200
2800
3260
2700
3000
1600
640
960
1560
1900
2170
1080
850
1340
1830
1930
1440
1000
940
1780
ORGANIC
NITROGEN
mg/1 N
13
17
15
13
17
14
15
16
86
84
56
125
130
170
10
330
100
120
110
80
130
80
80
90
100
120
110
160
160
140
140
100
50
90
100
50
40
40
80
80
110
410
1130
970
40
H M 6
250
310
330
290
330
310
290
470
1300
1550
1560
2270
2520
2750
2790
3750
2280
2560
2280
2040
1860
—
2560
2100
2200
2400
2020
2310
2960
3420
2850
3140
1700
—
1010
1650
2000
2220
1120
890
1420
1960
2040
1850
2130
1910
1820
PHOSPHATE
rag /I
P
44
61,
50
49
0.8
34
60
55
-------
TABLE 9; LOADINGS AND REMOVALS. CARBON REMOVAL UNIT
PERIOD
1-5 2/1-5
6-13 2/6-13
14-21 2/14-21
22-29 2/22-3/1
30-39 3/2-11
40-43 3/12-15
44-48 3/16-20
49-55 3/21/27
56-57 3/28-29
58-60 3/30-4/1
61-67 4/2/8
68-73 4/9-14
74-76 4/15-17
77-81 4/18-22
82-84 4/23/25
85-88 4/26-29
89-91 4/30-5/2
92-95 5/3-6
96-98 5/7-9
99-103 5/10-14
104-108 5/15-19
109-112 5/20-23
113-116 5/24/27
117-121 5/28-6/1
122-129 6/2-9
130-136 6/10-16
137-143 6/17-23
144-150 6/24-30
151-157 7/1-7
158-164 7/8-14
165-171 7/15-21
172-178 7/22/28
179-185 7/29-8/4
186-192 8/5-11
193-199 8/12-18
200-206 8/19-25
207-213 8/26-9/1
214-220 9/2-8
221-227 9/9-15
228-234 9/16-22
235-241 9/23-29
242-248 9/30-10/6
249-255 10/7-13
256-262 10/14-20
263-269 10/21-27
270-276 10/28-11/3
277-283 11/4-10
284-290 ll/ll-H/17
291-297 11/18-24
298-304 11/25-12/1
305-311 12/2-8
312-318 12/9-15
319-325 12/16-22
326-332 12/23-29
333-339 12/30-1/5
340-346 1/6-12
347-352 1/13-18
ORGANIC CARBON
Effluent 1
mg/1 C I
32
27
30
20
IB
22
16
19
25
35
144
47
44
94
66
82
66
57
150
53
140
62
48
90
130
270
40
24
53
41
72
Influent 1
Loading I
Parameter j
230
20
14
6
3
3
5
3
8
13
16
22
35
5
5
4
3
6
5
3
5
4
4
10
13
6
6
11
6
9
»4
a
"I
64
65
77
82
84
90
93
91
90
93
71
91
94
93
93
90
91
90
85
95
84
94
93
88
91
75
86
92
88
.
89
CHEMICAL 1
OXYGEN DEMAND
Effluent 1
mg/1 02 |
1700
950
800
700
690
620
1040
770
700
750
1000
790
840
1740
2400
2080
2740
1550
610
630
770
1100
1130
650
400
490
710
710
700
630
750
730
Influent
Loading 1
Parameter |
36
45
51
32
25
24
12
17
15
35
21
32
39
51
180
1000
470
820
480
150
340
1100
1500
320
46
16
14
17
12
10
11
Removal 1
42
65
65
60
56
49
60
65
65
59
72
67
73
66
72
65
59
63
67
67
73
66
58
68
84
76
72
82
81
72
73
FHENOUCS
w
c
«»ri •*
»•- 0
** M a
«H E 01
lu £
U K
O.I
0.2
0.2
0.4
0.1
0.1
0.0
124
0.2
0.1
0.2
1.0
0.1
0.2
0.2
5.0
0.6
0.6
0.3
0.2
0.2
0.2
0.2
*
0.3
0.2
0.2
0.3
0.2
0.2
1.0
1.2
11.
16.
0.2
-
0.2
0.2
0.6
4.3
0.4
0.1
0.1
0.2
0.1
0.3
0.2
0.3
0.2
[ Influent
Loading
1 Parameter
170
11
9
4
2
2
2
I
5
6
12
2
2
2
3
3
4
10
8
6
9
5
5
m
2
3
3
8
8
7
8
11
44
220
32
55
27
42
210
330
62
8
3
3
3
2
2
2
CYANIDE
Effluent 1
«g/l CS 1
0.6
0.9
0.7
0.9
1.1
2.1
3.4
2.0
1.3
3.2
1.6
1.1
1.5
4.1
4.9
3.2
2.7
3.6
5.8
7.6
4.7
10
20
5.2
7.0
7.0
4.9
5.2
8.6
4.0
3.7
5.0
5.6
5.0
6.0
5.4
3.5
4.5
4.7
4.5
6.7
5.6
3.4
1.7
2.1
4.8
4.8
9.6
3.0
2.6
4.1
5.7
6.3
5.5
4.6
5.1
5.3
1 Influent
Loading
Parameter
3
0.6
0.6
0.2
0.1
0.04
0.03
0.03
0.07
0.1
0.2
0.2
0.2
0.04
0.05
0.05
0.08
0.01
0.09
0.07
0.08
0.2
0.1
0.2
0.3
0.3
0.3
0.4
0.3
0.2
0.2
0.1
O.I
0.1
0.2
0.1
0.1
0.1
0.1
0.3
2
1
1
1
0.6
1.
4
5
1
0.1
O.I
O.I
0.1
0.0
0.0
0.1
r*
9
"I
54
74
87
78
68
22
10
84
30
67
86
77
54
36
64
70
73
68
63
76
40
26
76
76
74
62
68
50
73
72
74
72
71
67
66
82
50
48
70
55
65
57
15
48
52
70
18
40
35
32
59
48
58
43
49
56
THIOCYANATE
Effluent
mg/1 SCN
32
39
26
35
22
•17
12
86
64
79
113
22
164
86
198
180
340
240
154
160
170
170
.
190
250
220
270
140
270
390
1220
390
630
150
510
220
190
290
310
140
180
250
280
280
280
280
290
280
b
u «
S2S
1!
82
6
2
1
1
1
1
1
2
4
1
1
1
1
3
4
4
5
5
3
3
.
1
2
2
5
1
2
3
9
13
100
32
-
27
15
25
100
170
20
4
2
2
2
1
1
1
**
a
" 1
0
0
20
40
57
0
40
50
88
30
35
24
0
0
.
17
0
0
15
0
29
44
0
24
23
32
.
9
17
3
0
17
0
0
0
0
26
15
0
10
AMMONIA
1 Effluent I
k"
200
265
240
220
200
210
200
230
280
410
320
340
600
950
1220
1260
1190
1290
1700
1580
1780
1970
2370
1740
2500
2950
1940
1950
1880
1670
1550
2080
2090
1780
1830
1870
1480
1850
2320
2670
1630
2340
1350
510
760
1240
1610
1890
900
790
1090
1600
1760
1120
820
770
1680
1-4
CS
H I
17
9
24
24
28
33
34
16
35
30
30
34
23
21
19
14
16
15
20
26
14
17
8
23
10
14
11
20
13
15
10
12
16
12
13
19
22
16
17
18
40
22
16
20
21
20
15
13
17
7
19
15
9
22
18
18
6
TOTAL
(Effluent
mg/1 N
230
300
270
240
280
320
360
350
380
1000
1300
1350
1660
1890
2580
1800
3150
2040
2060
1930
1760
1700
.
2210
1860
1920
1940
1590
1960
2490
2820
1800
2470
1450
»
950
1310
t710
1950
970
850
1140
1640
1800
1520
1750
1660
1750
N
r*
ed
** 1
a.
18
3
18
4
3
25
•
23
16
19
27
6
14
10
19
15
14
9
.
14
11
13
19
21
15
14
18
37
23
15
-
6
21
15
12
14
5
20
16
12
18
18
13
4
56
-------
Ul
IOO-
90-
8O-
iu
Ul
u
(C
UJ
60-
50-
340
u.
z
20
IO-
0
i i i i i i i i i i i i i i i I i i •
2O 40 60 80 100 120 140 160 I8O 200 220 240 260 280 300 320 340 360
DAYS OF OPERATION
Fig.-5 - CARBONACEOUS REMOVAL UNIT
PERCENTAGE OF WASTE UNDER TREATMENT
-------
The actual influent-to the carbonaceous unit was not monitored for quality
parameters. Concentrations of cheraical constituents present in the in-
fluent were computed by multiplying the percentage of waste being treated
by the chemical quality of the undiluted excess ammoniacal liquor being
treated and tabulated in Table 5. The computed influent qualities are
given in Table 8. Any contribution to these constituents from the dilution
water is considered to be insignificant. Plots of the influent concen-
trations of organic carbon and chemical oxygen demand are given in Figure 6-
phenolics, Figure 7; thiocyanate, Figure 8: and ammonia and total nitrogen,
Figure 9. The abrupt changes in concentrations to which the unit was
subjected are apparent from these Figures.
One of the purposes of this experiment was to determine under field
conditions the operating capabilities and limits of the biological
process. In other words, more realistic design parameters were being sought
for the biological treatment of ammoniacal liquors than could be obtained
from small laboratory experiments. For many wastes, design parameters
for treatment are often determined by conducting a series of experiments
using acclimated organisms in which temperature, pH, and viable organism
concentration are the major variables. Ammoniacal liquor is a somewhat
unique waste in that, to date, raw liquor has never been treated success-
fully in a biological system without dilution. Thus, the percentage of
waste becomes an important parameter also. This additional variable
coupled with the unsteady quality of the raw waste already mentioned made
the experiment even more complex.
Host biological treatment experiments are monitored by computing a factor
called a loading parameter. This term combines several operating variables
which often assists in understanding the observed behavior of biological
systems. Several forms for the term exist but one which has proved to
be useful in explaining the results of laboratory studies can easily be
derived from a statement of mass balance for the system. For a process
operating at steady state this balance may be expressed as (Mass in) =
(Ilass out) + (Mass reacted) . Algebraically this expression becomes
QCI = QCE + ft V
where
Q = volumetric flow in the system,
Cj = influent substrate concentration,
CE = effluent substrate concentration,
C = substrate concentration in the reactor,
t = residence time in the reactor,
V = volume of the reactor.
58
-------
In
1400
I3OO-
1200 -
1100-
1000-
u
- 9OOH
O
CD
8OO-
7OO-
u
u
z 600 H
o
CK
o 500 H
^400-
u.
- 300-
200-
IOO-
O
ORGANIC
CARBON
20 40
—T~
6O
T
1
80 100 120 140
T 1——I 1 1 1 1—
160 ISO 200 220 24O 260 280 300 32O 340 360
DAYS OF OPERATION
Fig.-6- CARBONACEOUS REMOVAL UNIT
INFLUENT CONCENTRATIONS.ORGANIC CARBONaCOD
evi
O
- 8000 3.
E
I- 7000 z
6OOO Q
z
- 5000
>
x
O
4000 <
u
- 3OOO u
-2000
-1000
-------
2000-
1800-
-i
z I6OO-
-------
1200-
1100-
1000-
900-
u
V)
^ 800
E
u 700
<
< 600
o
o
T 500
UJ
40O-
300-
200 -
IOO -
0
i i i i i I * i i i i * * i i i • Ir^
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
DAYS OF OPE RATION
Fia.-S- CARBONACEOUS REMOVAL UNIT
INFLUENT CONCENTRATION THIOCYANATE
-------
4800-
4OOO -
32OO -
E 2400 -
z
UJ
o
o
a:
z I6OO
80O-
40
I I I i i
80 120 160 200 240
DAYS OF OPERATION
Fig.-9-EXCESS AMMONIACAL LIQUOR
CONCENTRATIONS TOTAL NITROGEN AND AMMONIA
28O
I
320
T
360
-------
For a complete-mix reactor as was used in this study, effluent concentra-
tions equal reactor concentrations (C = CE). In biological systems, the
rate of removal of substrate material is known to be proportional to
substrate and viable organism concentrations. This may be stated as
ft - KCS (4)
where
K = a proportionality constant and
S = viable organism concentration in the reactor.
Substituting equation (4) into equation (3) and reducing yields
QCCj - CE) = KCSV (5)
But since V/Q = t, the aeration time in the reactor, and Cj - CE = CR,
which is the concentration of substrate removed, equation (5) reduces to
C
sf = KC
The left-hand term of this equation defines the loading parameter. An
arithmetic plot of this parameter versus the effluent concentration of
substrate should provide a straight line x\rith a slope equal to the pro-
portionality constant K. This derivation assumed constant temperature,
proper oxygen tension, appropriate pH levels, satisfactory sedimentation,
and, in general, steady state operation. The proportionality constant
will vary with all of these and the results of the experiment will be
discussed in light of these variables.
In the experimental approach utilized to determine the limiting loading
parameter possible in the carbonaceous unit for the various substrates,
the system, after proper acclimation, was subjected to increased loadings.
System response was measured by monitoring the effluent and viable solids
concentration while maintaining a constant aeration time. As loading
increases, a point is reached beyond which system failure occurs. This
failure may be manifested by an appearance of excessive amounts of sub-
strate or other constituents in the effluent.
A major problem with the use of equation (6) is its failure to signify
whether the system is not fully acclimated or is experiencing failure.
63
-------
For example, in comparison to a system at steady rate, a system not
fully acclimated would show a low concentration of substrate removed and
a relatively high effluent concentration. After failure, the identical
condition exists. This deficiency may be overcome by modification of the
equation by converting it to an influent loading factor rather than one
based on substrate removal. This modified equation becomes
K • V, m
where Y^ is a modified constant which may vary slightly with removal
efficiency. This equation, although not as theoretically sound as
equation (6), does allow prediction of the particular mode in which the
unit is operating. The influent loading parameter varies directly with
influent concentration. At failure, this term will only reflect changes
in the concentration of viable solids in the reactor while the concen-
tration of substrate in the effluent will increase rapidly.
Values for this loading parameter are calculated and given in Table 9
for organic carbon, chemical oxygen demand, phenolics, cyanide, and
thiocyanate. These loadings are based on the influent concentrations of
each constituent as computed and given in Table 8. The reactor or aeration
time is constant for the entire experiment and is one (1) day. The viable
solids concentration in the reactor is taken as proportional to the result
of the Imhoff cone reading on the mixed liquor. This assumption may be
questioned on several points since the Imhoff cone technique measures the
volume of settleable solids and as such necessarily is influenced by the
settleability of the solids and does not differentiate between viable and
non-viable solids. However, the advantages of this quick and simple test
conducted routinely for process control by the operator proved to be an
adequate substitute for more widely accepted measurements of viable solids.
The loading parameter calculated using this substitute for organism con-
centration will be utilized in subsequent paragraphs to explain operational
fluctuations.
In addition to the computed loading factor, the status of operation may
also be judged by other parameters including quality of the effluent in
terms of contaminant concentrations (Table 9), percentage removals of
contaminants (Table 9), effluent loads, and by changes in reactor solids
concentration (Table 7). The purpose for the treatment of this waste is
to reduce the amount of contaminants in the waste discharge. Since waste
discharge effect receiving streams on the basis of mass of contaminants
dishcarged, the concentration of a constituent multiplied by the volumetric
flow rate is important. In the pilot plant, the flow rate was held con-
stant at one (1) gallon per minute so it can be neglected for comparative
purposes. However, the plant was operated with a diluted waste and the
64
-------
dilution factor becomes most important in determining the mass discharge
for a full-scale treatment plant. For example, treatment of 25 percent
waste with an effluent concentration of 10 mg/1 of some constituent dis-
charges a larger mass of material than one operating at 75 percent waste
and an effluent concentration of 25 mg/1. Tabulations of effluent dis-
charge loads for comparative purposes for organic carbon, chemical oxygen
demand, phenolics, cyanide, and thiocyanate are given in Table 10.
The carbonaceous treatment unit experienced during the operational period
of some 352 days several upsets or periods of poor operation. Using the
parameters and factors just discussed, the periods of smooth operations
and problems will be discussed in an attempt to derive guidelines for
design and operation of an ammoniacal liquor treatment unit.
The influent to the carbonaceous treatment units, for the first 55 days
of operation, was only about 15 percent waste. In addition, the waste
for the entire period was x*eak but was especially so for the first 40
days. This combination of high dilution and weak waste combined to pro-
vide a low influent loading. However, initially the concentration of
viable solids in the reactor was low so the influent loading parameter
was high. This, parameter decreased rapidly as the unit became acclimated.
On or about day 40, the strength of the waste in terms of organic carbon
and phenolics almost doubled. This was accompanied by a fall in reactor
pH resulting from partial nitrification of ammonia within the carbonaceous
removal unit. These changes were reflected in a decrease in reactor
solids but the unit continued to operate most satisfactorily as measured
by percentage removals or mass discharge of phenolics and organic carbon.
The percentage of waste under treatment was increased to approximately
25 percent beginning on day 56. This was reflected by a corresponding
increase in influent loads for organic carbon and phenolics. The system
was responding well. Unfortunately, on day 64 the reactor temperature
was found to be 123° F, far too high for this type of treatment unit.
System problems produced poorer percentage removals of organic carbon
(93 to 71), presence of phenolics in the effluent (124 mg/1), increases
in the amounts of these two constituents discharged, and a sudden decrease
in reactor suspended solids. Unit recovery was rapid for both organic
cajbon and phenolics but required almost two weeks for suspended solids
concentrations to increase substantially.
Corresponding to the sudden increase in reactor suspended solids came a
period of high influent organic carbon concentrations. The initial part
of this period was also accompanied by a reactor temperature increase from
about 80 to 85° F (days 82-91). This short period was a time of excellent
treatment with waste percentage at about 40 percent, low influent loading
parameters for organic carbon and phenolics, removal of over 90 percent
of the organic carbon and the best thiocyanate removal (88 percent) ex-
perienced during the entire test.
65
-------
TABLE 10; EFFLUENT LOADS PER UNIT VOLUME OF WASTE
,
Period
1-5
6-13
14-21
22-29
30-39
40-43
44-48
49-55
56-57
58-60
61-67
68-73
74-76
77-81
82-84
85-88
89-91
92-95
96-98
99-103
104-108
109-112
113-116
117-121
122-129
130-136
137-143
144-150
Percent
Waste
13
15
17
15
15
16
16
15
22
29
23
27
25
24
36
42
38
47
61
64
57
70
76
73
82
89
56
65
Mass Discharged,
mg/1 per unit of waste
cs
H
CO
o
u u
c
CO
oo
s
250
180
180
130
120
140
100
130
110
120
630
170
180
280
180
200
170
120
250
80
250
90
60
120
160
300
70
40
c
0)
00
>. «N
° ,
f-l TJ
CO C
o to
•H 8
B a
01 Q
CJ
1700
1200
*
CO
u
•H r-*
i-( O
§c
11
it f,
f* PU
PL,
0.8
1.3
1.2.
2.7
0.7
0.6
-
-
0
-
54.
0.7
-
0.3
-
0.5
-
2.1
-
0.2
0.4
-
0.3
7.0
0.7
0.7
0.5
0.3
„
o>
•o
a
tfl E5
^>U
O
5
6
4
6
7
13
21
13
6
11
7
4
6
12
14
8
7
8
9
12
8
14
26
7
9
8
9
8
0)
4J
s
to
;*>
u
OK
-H CJ
H
250
260
150
230
150
110
-
-
55
-
370
240
-
230
-
270
-
47
-
260
150
-
260
250
-
380
430
240
Period
151-157
158-164
165-171
172-178
179-185
186-192
193-199
200-206
207-213
214-220
221-227
228-234
235-241
242-248
249-255
256-262
263-269
270-276
277-283
284-290
291-297
298-304
305-311
312-318
319-325
326-332
333-339
340-346
347-352
Percent
Waste
60
54
49
72
78
74
74
74
86
71
68
79
81
75
40
17
23
43
47
58
30
22
35
45
45
58
49
46
47
Mass Discharged,
mg/1 per unit of waste
u
o
h
CO
o
o
•H
CO
oo
O
90
0)
00
>> CM
^
rH ^0
to c
o to
e v
0 0
6
1200
1300
1300
1400
1000
900
1000
1400
900
2600
2600
3000
2600
3700
3900
3600
2700
1800
2300
2000
2200
1800
1400
1600
1600
1200
1300
1600
1600
-
•H rH
r-t O
O C3
C 0)
0) .C
p,
0.3
0.4
0.4
-
0.4
0.3
0.3
0.4
0.2
0.3
1.5
1.5
14.
21.
0.5
-
0.9
0.5
1.2
7.4
1.3
0.5
0.3
0.4
0.2
0.5
0.4
0.7
0.4
HI
•o
g
g"
u
14
7
8
7
7
7
8
7
4
6
7
6
8
7
9
10
9
11
10
17
10
12
12
13
14
9
9
11
11
M
QJ
iJ
S
CO
•^ C/3
H
270
310
350
-
240
340
300
370
160
380
570
1500
480
840
370
3000
960
440
620
530
470
820
710
620
620
480
570
630
600
66
-------
This short period was followed by a decrease in reactor temperature by
almost 10° F over a period of about one week. This may have accounted
for the appearance of phenolics in the effluent (1 mg/1) and a decrease
in reactor solids. Concurrently, the waste percentage under treatment
rose to about 60 percent which increased loadings on the unit.
The period between days 99 and 116 was characterized by increasing waste
percentages being treated (60 to 75), reactor temperatures about 85° F,
good reactor dissolved oxygen concentrations, and overall good removals
of major constituents. The slow decrease in reactor suspended solids is
believed due to the increase in organism'activity resulting from increased
temperature.
i
The system for the period 117-121 suddenly showed a phenolics concentration
of 5 mg/1 which was followed by a decrease in reactor solids during the
next few days. No definite reasons for this system failure can be estab-
lished but certain observations may be significant. Cyanide concentrations
in the raw waste, the unit's influent, and in the effluent had been
increasing. During the averaging period just prior to that of failure,
cyanide concentrations in the reactor had increased from 10 to 20 mg/1.
In addition average reactor dissolved oxygen concentrations had decreased
from 4.1 to 2.8 mg/1. The most plausible explanation probably involves
the presence of cyanide.
The period from 122-136 was characterized by low reactor suspended
solids and increasing percentages of waste treated. The maximum per-
centage treated was 89 percent. These two factors combined to increase
the influent loading parameters for organic carbon and phenolics. Un-
fortunately, on day 136 the reactor-dissolved oxygen concentration was
found to be only 0.2 mg/1 which is not considered an adequate level for
aerobic treatment. Unit failure is indicated by the low percentage re-
movals of chemical oxygen demand and sudden reductions in reactor sus-
pended solids.
Operations during the interval between day 136 and 172 utilized between
50 and 60 percent waste and the waste during this period was moderately
weak. The rather low influent loadings along with reactor temperatures
of almost 90° F combined to limit the reactor suspended solids to low
levels. Overall the interval was marked by excellent removal of phenolics,
probably the best sustained removals of cyanides, only fair removal of
chemical oxygen demand, but low mass discharge of COD.
Percent waste being treated x*as increased on day 172 from about 50 to 75
and was held at this level for about 75 days. The first half of this
period was characterized by slowly increasing influent loads of chemical
oxygen demand and phenolics. Unit operation was comparatively steady up
until day 214 with temperature suspended solids at satisfactory levels.
Only occasional marginal dissolved oxygen concentrations were noted and
these apparently caused no major operational problems. During this period,
the unit treated its highest waste concentration in which reactor foaming
was easily controlled. Removals of phenolics were excellent with removals
67
-------
of COD and cyanide of about 60 and 70 percent, respectively. Little or
no removal of thiocyanate was experienced which was especially disappointing.
On or soon after day 214 the strength of the raw waste in terms of chemi-
cal oxygen demand, phenolics, and thiocyanate suddenly increased by
factors of 1-1/2 to almost 4. With essentially a constant percentage
of waste in the feed, the unit was subjected to a rather large change
in loading. However, the unit continued to remove both COD and phenolics
although foaming in the reactor became a problem. From the data, it
appears that the unit could have survived this shock loading. Unfortunately,
however, the unit in the succeeding weeks was subjected to ever-increasing
loads and on at least day 223 to low dissolved oxygen levels and on one
day (228) reactor thiocyanate reached 1220 mg/1. The units suspended
solids concentrations and its removal of chemical oxygen demand were
satisfactory. Actually, only foaming and effluent phenolics concentrations
of about 1 mg/1 gave indications of problems. A decrease in average re-
actor temperature from 90 to 78° F over the periods from days 228 to 248
caused major problems including loss of reactor solids and excessive ef-
fluent phenolic concentrations.
After unit failure, on day 249, the percentage of influent in the waste
was decreased in an attempt to restore performance. Both phenolics and
chemical oxygen demand removals improved and from an effluent load view-
point the unit performed well. The decrease in waste feed percentage was
accompanied by a decrease in the raw ammoniacal liquor concentration of
phenolics from over 2000 mg/1 to 650 mg/1 and although a corresponding
decrease in COD did not occur immediately, a trend to lower COD levels
in the raw liquor was established. Reactor temperatures continued to be
low (minimum recorded was 61° F, day 289) until about day 300. The most
notable problem during this period was the inability of the unit to accumu-
late organisms. Treatment efficiency, as measured by effluent quality and
mass discharge for phenolics and COD were good. The unit apparently x*as
acting essentially as an aerated lagoon. The major differences between
a complete-mix activated sludge system and an aerated lagoon is that in
the lagoon no suspended solids are separated from the effluent and re-
turned to the reactor. During this period, this unit operated on this
basis since little difference is noted in the concentrations of solids
in the mixed liquor and return sludge. In other words, the return sludge
was the same as the mixed liquor. This indicates a diffuse, growth which
settled poorly and contributed to turbid effluent as indicated by rela-
tively low Seechi disk readings during the oeriod. This turbidity also
contributed to the effluent COD. This ability of the system to operate
insofar as COD and phenolics are concerned as an aerated lagoon under
the adverse conditions of low temperature and at only a detention time
of 24 hours is most remarkable and should be pursued further.
Attempts to reconvert the system to an activated sludge regime included
reseeding of the system about day 260 without success and increasing the
reactor temperature around day 300. This latter effort along with a
decision to operate the unit at a steady waste feed concentration of 50
percent brought about an almost immediate increase in reactor solids and
68
-------
in sludge returned. Phenolics removal continued to be good and some im-
provement in COD is noted, at least part of which is due to a less turbid
effluent.
In summary the carbonaceous removal unit performed well during much of
the test period. Several unfortunate occurrences upset operation but
much was learned from these disturbances. Table 11 summarizes the opera-
tional parameters and results during those periods of selectively stable
operation. Treatment of up to 75 percent raw ammoniacal liquor was demon-
strated in a plant operating with an aeration period of 24 hours at tem-
peratures from 75 to 90° F. Influent concentrations or organic carbon,
chemical oxygen demand, phenolics, and thiocyanate vary considerably from
period to period and do not vary in direct proportion to the percentage
of waste under treatment. This indicates the variability in the raw
waste under treatment.
Two interesting points concerning the loading parameter are x^orthy of
note. First, levels of 4 to 5 for the organic carbon factor at reactor
temperatures of 80 to 85° F appear to be easily treated as judged by
percentage removals or organic carbon and phenolics as well as low mass
discharges for these constituents. Neglecting the period between 249
and 304, the influent loading parameter for chemical oxygen demand appears
to be inversely related to the percent removal of COD. Phenolics loading
parameters of around five did not cause problems. The second point of
interest is the period between 245-304 when comparatively large values
for loading parameters were encountered but reasonably good treatment was
attained. This apparently occurred when the unit, probably because of
lower operating temperatures, began producing a diffuse biological growth
which did not settle. The unit effectively became an aerated lagoon.
During this interval the mass discharges of both phenolics and chemical
oxygen demand were somewhat greater than when the unit was operating as
an activated sludge unit. However, the degree of treatment was surprising
considering only a 24-hour aeration time.
The removal of thiocyanate was most discouraging throughout the test.
The percentage removal of this constituent seems to decrease as influent
waste strength increases. From some recent laboratory work, indications
that thiocyanate removing organisms are relatively sensitive and are
slow growers has been found. Thus, although some suitable organisms
were originally present and became partially acclimated, unit upsets
and loadings discouraged the development of the thiocyanate organisms.
Removals of cyanide ranged from about 50 to 70 percent. The reasons
for only partial removal of cyanide are not known but it is hypothesized
that the remainder is in a form not amenable to biological oxidation or
air stripping such as possibly a metallic complex or organic compound.
Table 12 summarizes the failures which were experienced by the unit, how
the failure was recognized, and the possible cause or causes of the
failure. In all, five major failures occurred and caused varying degrees
of problems including excessive foaming in the reactor; increases in
69
-------
TABLE 11: SUMMARY OF CONDITIONS DURING PERIODS OF UNIT STABILITY
Period
22-55
82-91
99-116
137-171
172-213
249-304
312-352
OPERATING CONDITIONS
01
4-1
CO
CO
:»
jj
c
o> "
o
H
0>
eu
15
40
70
55
75
35
50
fe
o
^
V
V.
3
4-1
CO
Vl
(1)
I-
01
H
80
85
85
90
90
75
90
INFLUENT
Concentrations,
mg/1
o
O "
•H a
c o
CO .0
00 fc
k CO
O 0
180
840
930
-
-
-
-
i
0)
«-l Q CM
CO O
u a
•H 01 •
S oo-o
v xc
43 X CO
uo e
-
-
-
1800
2200
2500
3000
A
ta
u
•r* t-4
i-l O
o c
C 01
01 X
4= P-.
Pk
100
350
500
330
550
370
570
o>
4-t
§
CO
>s
U Z
0 O
i-l CO
.C
H
40
230
150
180
220
210
310
Loading
1 1 ^
Parameterv '
u
•H C
a o
CO .0
00 l-i
jj CO
o y
4
5
4
-
•
-
-
r-l
CO C
U 0) *O
•* oo c
E >, co
Jg§
U Q
-
•
-
38
21
650
13
(0
u
••-i
i-H
O
c
01
FU
2
2
3
7
5
110
3
OPERATING RESULTS
nvsin fvtfvfnn n TTum j A T O
PERCENT REMOVALS
C
£>
M
3
u
•I-l
CO
00
M
O
88
92
92
-
-
-
«•
1-1
ce G
O *
o
O
•1-1
J3
H
50
50
30
30
15
10
10
01
•o
•r«
C
CO
>,
O '
45
55
50
65
70
,40
50
MASS ,.
T^T G/"*U A 'D/^C'C' V ^ /
DISCHARGES
C
o
JO
M
CO
U
0
•r-l
c
CO
00
M
O
120
180
120
-
-
-
-
^^
cdc
Udi*n
w w
•HOOC
g^>». M
p^TO
i«t c
?s t
J=O 0)
r 1 /"I
U t-4
-
-
-
1300
1100
2500
1500
(0
u
•H
i-4
0
C
0)
PH
1.0
.0.5
0.3
0.4
0.3
1.7
0.4
-J
o
(!) See text for units..
-------
TABLE 12: SUMMARY OF TREATMENT UNIT FAILURES
PERIOD
Manifestations
Possible Causes
61-67
89-91
117-121
130-136
214-248
Reduction in % removal, organic carbon
Phenolics present in effluent
Increase in mass discharges
Decrease in reactor Suspended solids
\" J
Phenolics present in effluent
Decrease in reactor suspended solids
Phenolics present in effluent
Reduction in % removal, organic carbon
Increase, effluent cone., organic carbon
Decrease in reactor suspended solids
Excessive reactor foaming
Low,but unsatisfactory levels of phenolics
Low concentrations of reactor suspended solids
High reactor temperature,
123°F, day 64.
Temperature decrease accompanied
by increase in loadings.
High reactor cyanide levels,
up to 20 mg/1.
Decrease in reactor dissolved oxygen.
Low reactor dissolved oxygen.
Increase in load.
Large increase in load .
High reactor thiocyanate concentrations.
Low reactor dissolved oxygen,
intermittently.
Decrease in reactor temperature.
-------
effluent concentrations and reductions in percent removals of organic
carbon, COD, and phenolics; decreases in levels of reactor suspended solids;
and increases in mass discharges of COD. These problems were caused by
increases and decreases in reactor temperature, sudden or large increases
in loadings, low reactor oxygen levels, and possibly high concentrations
of cyanide and thiocyanate. In investigating these failures, not one
single case of failure resulting from slow increases in loading was
obtained. Thus, maximum possible influent loadings were not necessarily
attained.
NITRIFICATION UNIT
The major nitrogenous component in excess ammoniacal liquor is ammonia.
In addition, there are smaller amounts of combined nitrogen in organic
compounds and thiocyanate. As a result of nitrification in the carbonaceous
unit varying amounts of nitrite and nitrate may also be present. In
addition to discussing the specific nitrogenous species, a term encompassing
all measured forms of nitrogen called total nitrogen is used. Essentially,
total nitrogen, as used here, includes that present and measured as ammonia,
organic nitrogen, cyanide, nitrite, and nitrate. Thiocyanate-nitrogen is
not included as a separate item because it is determined as part of the
organic nitrogen fraction.
The nitrogenous composition of the excess ammoniacal liquor utilized during
the pilot plant study is given in detail in an appendix and summarized in
Tables 5 and 6. Figure 9 graphically presents the ammonia and total nitrogen
contents of the waste. The total nitrogen curve is not continuous because
of insufficient data for all averaging periods for all of the components
which are included in this category. As can be seen, the major nitrogenous
component by far is ammonia except for two consecutive averaging periods
near the end of the experiment. For these periods, total nitrogen was
essentially divided equally between ammonia and organic nitrogen. No
satisfactory explanation for this anomalous behavior has been found. In
addition, note should be made of the sudden and large changes in ammonia
and total nitrogen content of the waste. Changes by factors of abovit two
in the concentrations of these constituents apparently occur with some
regularity.
Some apparent removals of nitrogenous components and some interconversions
between the various nitrogen-containing compounds take place x-rithin the
carbonaceous removal unit. Activated sludge plants treating municipal
sewage remove from 50 to 85 percent of the organic nitrogen fraction and
15 to 75 percent of the total nitrogen. Nitrogen removals take place
by many mechanisms which include coagulation and sedimentation of colloids
containing nitrogenous components, especially organic nitrogen; volatili-
zation; and, incorporation into cell substance. Interconversions between
forms result from the hydrolysis of organic nitrogen compounds to ammonia
and the oxidation of ammonia to nitrite and nitrate. If the oxidation of
72
-------
ammonia takes place, then the loss of nitrogen through denitrification is
also possible. These same processes are operative in the treatment of
aramoniacal liquor in the carbonaceous removal unit. According to the infor-
mation given in Table 9, removals of ammonia in the unit ranged from 6 to
40 percent and averaged about 19 percent; total nitrogen removal ranged
from 3 to 37 percent and averaged about 15 percent. Unfortunately,
nitrite was not determined routinely on the effluent from the carbonaceous
unit which casts some doubt on the validity of these removals. Further
discussion of this point will be given later in this section.
The second stage of the pilot plant operation, the nitrification phase,
was started on January 8 and was initially fed ammonium sulfate and
phosphoric acid in an attempt to develop a population of nitrifying
organisms. On January 29, the system was converted to a continuous feed
of one (1) gallon per minute of carbonaceous effluent. This flow rate
represented approximately 24 hours of aeration time. On February 1,
collection of routine analytical and operational data commenced and the
ensuing discussion covers the period subsequent to this tine.
The operating conditions for the nitrification unit are given in Table
13 for averaging periods closely corresponding to those used for the
carbonaceous unit. Special attention is called to those periods when
the unit was receiving carbonaceous unit effluent, artificial ammonium
sulfate and water, and when a combination of the two was being treated.
The many changes between operating modes were made because of the varying
conditions of the carbonaceous units effluent. Most of the changes were
precautionary in that this unit ^as converted to artificial ammonia before
major changes in the carbonaceous unit were made. This was done in order
to avoid possible upsets in the nitrification unit resulting from sudden
changes in the carbonaceous unit's effluent.
The concentration of viable organisms in this unit remained low at all
times despite the fact that no sludge was intentionally wasted. This
was somewhat expected in view of the slow growth rate characteristics of
the organisms and their relatively poor efficiency in converting inorganic
carbon compounds to cell bodies. According to the limited data available,
mixed liquor suspended solids probably never exceeded 1,000 mg/1. The
Imhoff Cone measurements indicate these low levels also. However, com-
parisons of the Irahoff Cone measurements between the mixed liquor and
return sludge point out that the settleability of the sludge was good
for most periods. The Seechi Disk measurements also indicate that the
effluent was reasonably clear and free of non-settleable solids.
A major factor of importance to autotrophic bacteria such as the nitrifiers
is an available source of inorganic carbon. This carbon can be supplied
as carbon dioxide, bicarbonate, or carbonate. These forms of carbonic
acid are interrelated through the ionization constants for the acid and
the pH. In natural waters, the quantities of these constituents can often
be estimated through the determination of alkalinity and pll. Computations
73
-------
13:
OPERATING CONDITIONS NITRIFICATION UNIT
Period
2-6
7-14
15-22
23-30
31-40
41-44
45-49
50-56
57-58
59-61
62-63
66-69
70-74
75-77
78-82
83-85
86-89
90-92
93-96
97-99
100-102
103-104
105-107
108-115
116-121
122-130
131-137
138-144
145-151
152-156
157-158
159-165
166-172
173-179
180-186
187-193
194-200
201-207
208-214
215-221
222-228
229-235
236-242
243-249
250-251
252-256
257-263
264-270
271-277
278-284
285-291
292-298
299-305
306-312
313-319
320-326
327-333
334-340
341-347
348-352
Influent ,
Percent
01
3
O
u £
CO Q)
C 3
0 *-4
.Q UJ
(0 fj]
O
100
100
100
100
100
100
100
100
100
100
LOO
100
100
100
100
100
100
100
100
100
100
25
30
35
25
15
,j
(U
4j
n)
100
100
100
100
100
100
100
100
100
75
70
65
75
100
100
100
85
r-4
60
•a
i— 1
O
en
"O
a
•o
c
X.
tn
3
C/J
J
-•
510
830
540
610
310
420
70
150
o
41
3
n
u
Q.
£
H
82
81
81
83
83
79
82
82
82
83
85
86
90
93
91
94
96
86
85
90
94
91
88
92
92
89
95
95
95
95
95
96
96
95
96
95
95
96
x
a
6.9
7.1
7.4
6.9
7.3
7.3
6.9
7.2
7.1
7.0
7.4
6.6
6.5
7.3
7.1
7.1
7.4
7.2
7.9
8.3
6.8
8.2
7.8
6.8
7.8
8.0
7.1
6.9
7.3
8.0
6.4
6.9
6.9
7.8
7.5
6.6
6.7
8.1
PI
o
u
u
1?
M
4J
•f"*
c
•H
It
<
90
130
150
130
150
130
120
120
150
140
130
45
50
110
90
110
160
140
530
520
80
350
240
50
270
210
70
60
100
180
25
40
50
200
110
40
40
220
^-4
t
c
01
CO
x'
o
TD
>
1—4
o
Vt .
in
a
3.4
3.1
2.6
2.0
3.0
2.9
2.7
2.0
2.5
2.6
3.0
3.3
3.1
1.7
1.9
Irohoff
cone , t
ml/1
g
3
cr
•r*
•J
•a
*
5
6
5
9
3
13
17
16
21
25
33
26
32
22
28
24
24
25
14
13
5
9
4
4
6
2
2
2
3
3
4
3
3
3
3
3
1
1
a
oo
•0
3
i— i
in
c
3
It
a:
8
10
15
20
28
28
43
44
47
66
57
63
39
58
56
50
54
30
25
13
17
7
8
12
3
4
6
7
6
8
11
5
7
4
3
5
(41
dj
_c
u
c
Vt
•**
Q
•*4
.C
U
U
Vj
4
3
4
5
8
8
10
6
5
6
5
9
9
6
5
5
5
4
5
6
7
5
10
4
7
10
16
20
18
11
11
9
5
9
10
18
9
Additives per period
pounds
-V.
^
E£
.2
•o
o
7
23
31
22
35
95
122
92
61
17
6
67
92
2
78
52
9
ml.
V
1
O
—
D-.
>— 4
's •
*J
3
.2
H
4
12
9
6.
4
16
1
•u
u
.^
M
o
w
c
f
£
300
100
1650
400
1400
1400
1000
200
1300
1400
1200
14
14
12
12
14
z,
8
14
14
14
14
14
14
14
14
12
12
14
6
14
12
100
107
110
100
77
35
63
153
125
105
U
)4
80
74
122
97
41
107
90
46
38
40
1OO
80
40
30
Comments
.
i
'-
,
Temp. drop.
Alk. increase.
,
Jligli pH caused
by low 02-
74
-------
based on this simple model would indicate large amounts of inorganic
carbon present in the excess ammoniacal liquor. However, in the case of
this waste with its large concentration of ammonia and pi! values of
roughly 8.5-9.0 it can be easily shown that the apparent alkalinity as
determined is almost all due to the ammonia and that inorganic carbon
levels are relatively low. However, in subsequent treatment stages when
ammonia concentrations, decrease either through treatment or dilution and
the pll decreases, the alkalinity determination does become a measure of
the inorganic carbon content. By reference to Appendix A-2, the alkalinity
of the carbonaceous units effluent is seen to vary widely. However, if
ammonia alkalinity is neglected, the carbonaceous alkalinity is normallv
only a few hundred parts per million as calcium carbonate. This represents
only a small concentration of inorganic carbon. The conclusion is quickly
reached that the waste cannot supply the necessary inorganic carbon
directly and that this constituent must be supplemented.
A possible source of inorganic carbon would be that produced as consequence
of the oxidation of the organic carbonaceous material in the first treat-
ment unit. According to the data in Table 5, the organic carbon content
of the raw waste may be as high as 3,000 mg/1. Unfortunately, even
though most of this is converted to inorganic carbon, the inorganic carbon
is mostly lost as carbon dioxide. To prevent this loss would require
pH values in excess of operational limits. However, conservation of
inorganic carbon is enhanced by high pll and every effort should be made
to operate this unit near the maximum operational pll.
Supplementary inorganic carbon has been required in all laboratory tests
as well as in the pilot unit for the nitrification of excess ammoniacal
liquor. Sources of inorganic carbon have included limestone, calcium
carbonate, and soda ash. Powdered limestone has worked well in the
laboratory but only limited experiments were attempted in the field.
Sodium carbonate was used almost exclusively because of its effectiveness
and ease of handling. The addition of inorganic carbon to an aerated
solution such as is encountered in the nitrification unit can lead to loss
of the carbon as carbon dioxide depending upon the pH. As the pH decreases
from 8, the rate of loss increases. Since the nitrification reaction tends
to decrease the pll, control of this parameter is necessary. Several
chemicals including hydrated lime, burnt lime, "and sodium hydroxide were
used for the purpose with sodium hydroxide proving to be most suitable.
An attempt to provide a more quantitative view of the alkalinity rela-
tionships in the nitrification unit is given in Appendix C.
Phosphoric acid was added to the unit during periods when an artificial
feed of water and ammonium sulfate were being treated to supply the
biological process with the nutritional necessity, phosphorus.
Phosphorus, during treatment of ammoniacal liquor, was present in the
effluent from the carbonaceous unit. Tributyl phosphate was occasionally
added as an antifoaming agent.
75
-------
The basic purpose of the nitrification unit is to produce, nitrite and
nitrate from the incoming nitrogenous constituents. Actually, the true
autotrophic nitrifiers are capable only of oxidizing ammonia. However,
since no practicable way of limiting the biological activity of the
flora in this unit to the autotrophs was available, changes in other
nitrogenous constituents is also possible. For these reasons, several
approaches to calculating the efficiency of the unit are available
and along with the operating results are summarized on Table 14.
Data for four periods are not included because of unsteady operations
resulting from changes between, carbonaceous effluent feed and artificial
ammonia feed in such a way that the changes could not adequately be
monitored. In addition, one period was experienced when flow disruptions
occurred and the data obtained was not considered representative. The
data for periods in which reasonable steady operation was experienced
is given.
The first several columns of Table 14 give the nitrogenous components
present in the influent to the nitrification unit. These nitrogenous
components come from carbonaceous effluent and/or ammonium sulfate.
The effluent from carbonaceous unit was monitored for ammonia, organic
nitrogen which includes thiocyanate nitrogen, and nitrate nitrogen.
The "total" nitrogen listed as being contributed by this source is the
sum of these three components and unfortunately does not include nitrite.
When the unit was operating on 100 percent carbonaceous effluent, these
concentrations equal those given on Table 9 for the effluent from
carbonaceous removal. When, according to Table 13, the unit was treating
a diluted carbonaceous effluent the influent nitrogenous concentrations
are computed using the appropriate percentage and the analysis of the
effluent for that period.
The computation of the concentration of ammonium sulfate in the influent
during those periods of its use are based on the flow of water and/or
waste and the weights of ammonium sulfate added per period as given on
Table 15. Influent total ammonia and total influent nitrogen are the
sums of the respective constituents x-rithout regard to source. Table 14
also gives a summary of the nitrogenous materials in the effluent from
the nitrification unit including ammonia, nitrite, nitrate, total
oxidized and a total. In this instance, organic nitrogen determinations
were not conducted. As nitrite and nitrate are the designated end products
of this unit their concentrations are most important.
The purpose of this unit is to oxidize ammonia to nitrite and nitrate.
One way of judging this activity is to observe the amount of ammonia
removed. A column for the percent of ammonia removal is given in
Table 14. This indicates that removals up to 90 percent were experienced
at times but probably something like 60 nercent was more common. Since
ammonia which passes this phase of treatment unoxidized will not be
76
-------
TABLE lit
NITRIFICATION UNIT. SUMMARY
PERIOD
2-6
7-14
15-22
23-30
31-40
41-44
45-49
50-56
57-58
59-61
62-74
75-77
78-82
83-85
86-89
90-92
93-96
97-122
123-130
131-137
138-144
145-151
152-158
159-165
166-172
173-179
180- 186
187-193
194-201
202-215
216-221
222-228
229-235
236-242
243-249
250-256
257-263
264-270
271-277
278-284
285-291
292-298
299-305
306-312
313-319
320-326
327-333
334-340
341-347
348-352
Nitrogenous materials, mg/1 as nitrogen
I n f 1 u
By source
Carbonaceous Effluent
CO
C
i
"*1
200
26O
240
220
200
210
200
230
280
410
600
950
1220
1260
1190
1290
500
540
520
460
580
670
410
580
130
190
310
400
470
220
200
270
400
440
280
210
190
420
c
fj Hi
•rJ QQ
n o
nj ij
ao *j
0 Z
30
30
30
20
20
20
20
-
-
50
40
-
60
.30
50
30
40
40
20
20
-
20
20
20
20
20
20
10
10
10
100
230
230
20
c
01 V
^* 00
CO O
hJ It
z z
o
0
0
1
70(''
90(U
60
70
60
70
CM
\^
CO
0
H
230
290
270
240
290
320
-
360
-
e n t
•" &
U VI
ifci CM
*J '•J
U X
< Z
0
0
0
0
0
0
0
0
0
0
=p
ca C
ij O
O E
H E
200
260
240
220
200
210
200
230
280
410
CM
^ C
at
-< oc
CO o
0 u
230
290
270
240
Effluent
c
o
e
190
220
170
160
2W(-1' 120
320<1) 160
360
230
220
220
310
Oxidized
a
%
Z
z
40
48
56
61
77
69
69
76
110
127
4J
OJ
i^
£
40
53
71
70
89
87
91
108
87
114
_
2
o
H
80
100
130
130
160
150
160
180
200
240
c**
CO
w
!*
270
320
300
290
280
330
390
400
420
550
INTERMITTENT USE OF ARTIFICIAL AMMONIA ADDITIONS
1
5
6
5
5
7
1010
-
1310
1360
0
0
0
0
0
o
600
950
1220
1260
1190
1290
-
1010
1310
1360
190
710
610
740
550
660
230
215
185
344
396
192
103
182
115
348
441
214
330
400
300
690
840
410
520
1110
910
1430
1390
1070
INTERMITTENT USE OF ARTIFICIAL AMMONIA ADDITIONS
0
0
0
O
320
230
430
430
320
230
430
430
320
230
430
430
210
50
120
50
3
67
156
230
4
64
145
200
7
130
300
430
220
180
420
480
_
O
COS
V
(JfB
we
RJ O
I
5
15
29
27
40
14
-
21
24
68
25
50
41
54
49
34
78
72
89
INTERMITTENT USE OF ARTIFICIAL AMMONIA ADDITIONS
0
0
530
590
0
0
0
0
0
0
230
210
210
5OO
540
520
230
210
210
530
590
-
230
210
210
230
330
1000
200
120
70
F L 0 « DISRUPTION AND pH PROBLEMS
0 . 490
0
0
0
0
620
710
430
600
0
0
0
0
0
460
580
670
410
580
INTERMITTENT
0 . - 360 490
0
0
0
0
0
0
0
0
0
0
0
0
0
210
330
420
490
240
220
280
410
450
380
440
420
440
330
110
160
170
210
210
220
10
0
0
0
0
0
520
420
560
640
430
410
490
410
440
280
210
190
420
490
620
710
430
600
190
330
380
250
240
149
135
46
25
49
41
101
210
241
257
227
112
138
40
26
37
37
103
176
188
221
288
260
270
90
50
90
80
200
390
430
48O
510
490
600
1090
250
210
150
390
720
810
730
750
54
39
13
43
67
59
42
43
39
59
USE OF ARTIFICIAL AMMONIA ADDITIONS
-
540
440
580
660
450
430
500
420
450
380
440
420
440
50
130
150
510
400
110
70
110
80
190
50
140
360
470
326
267
152
0
0
0
154
263
210
140
222
209
62
127
366
335
189
58
83
128
201
197
204
131
243
231
112
171
690
600
340
60
80
130
350
460
410
270
460
440
170
300
740
730
490
570
480
240
420
570
490
460
510
580
530
770
90
75
64
10
37
75
83
78
80
58
82
33
-
C "D
Cu CU
a N
C ?
U X
o
0 C
cw
4J Ofi
C O
a> t*
o w
a»
30
31
43
45
57
46
41
45
48
44
64
36
33
48
60
38
3
72
72
90
53
45
8
20
43
53
51
54
53
66
67
93
82
69
10
17
54
83
81
84
59
90
76
32
40
?
C
y
00
o
.,4
CO
O
H
250
310
330
290
330
310
290
_
_
300
.
550
_
560
320
230
430
430
61O
650
-
230
210
210
580
740
850
710
780
-
580
520
660
720
490
430
570
500
510
460
530
480
450
c
oo
*
z «
O
C
01
CJ
-------
TABLE
OPERATING CONDITIONS, DENXTRIFICATION UNIT
(Influent * constant I gpm of nitrification effluent unless noted)
Period
3-7
8-15
16-23
24-31
32-41
42-45
46-50
51-57
58-59
60-62
63-75
76-78
79-83
84-86
87-90
91-93
94-97
98-123
124-131
132-138
130-145
146-152
153-159
160-166
167-173
174-180
181-187
188-194
195-202
203-216
217-222
223-229
230-236
237-243
244-250
251-257
258-264
265-271
272-278
279-285
2 86- 2 02
2<)3-20s
4J
B
•14
f_4
n
J£
<
140
230
180
270
350
300
370
400
440
580
•^
tf
8
BO
1
T3
r-l
o
w
to
O
2.6
Imhofr
Cone,
nig /I
k<
o
3
cr
J
-a
0
X
S
19
38
29
23
5
4
3
2
2
0>
00
•o
3
(/!
C
k4
3
01
od
35
40
40
48
7
5
3
3
5
6 ' 7
to
0)
JS
2
•*4
M
at
•H
a
>r4
.£
U
U
w
5
4
4
3
4
5
3
3
2
2
X
1
s<
A
O
1
0
GQ
2
2
USE OF ARTIFICIAL
360
380
420
290
440
840
1
2
4
2
0
3
4
8
1
1
3 ' 3
4
3
3
3
2
3
I1 S T OF ARTIFICIAL'
230
390
470
510
470
520
480
390
260
340
190
-
0.1
0.8
".1
0.6
0.2
0.2
1.1
u.O
0.0
0.2
2
1
1
1
1
0
1
3
5
3
5
•y
4
2
1
3
3
12
1
2
3
4
4
4
4
-
3
3
4
4
Special
Problems
00
c
t4
E
4
f\
S
y
a
•r4
M
r-4
.3
CO
X
X
X
|
b
u
C
V
3
U4
c
M
X
X
i
16 2
X
X
X
X
V
I T 2
•^ Dark color, bad odor.
X
Intermittent molasses flow.
L1 s F ;> F A R T I F i c I A i MI, i :: u :: T 2
030
1080
980
350
510
560
620'
850
870
680
830
780
3»«"" SS-AvR.
115mg/l.
i
!
78
-------
removed by later stages of treatment, the low percentage obtained limits
the overall removal potential for the plant. However, the plant was not
operated to produce a consistent effluent because of the many variations
in treatment schemes used in both the nitrification and carbonaceous
units. Therefore, more normal operation should be expected to approach
the maxima rather than the average obtained in such an experiment.
Fairly steady operation for the periods near the experiments end possibly
indicate that 75 to 80 percent ammonia removal might be anticipated.
Another way of looking at the operation of the nitrification unit is to
compute the percentage of the effluent nitrogen that is oxidized.
According to the column so labeled, values ranging from less than 50 to
more than 90 percent were experienced. Since only oxidized nitrogen
is capable of removal in the denitrification unit, the percentage
oxidized places an automatic upper limit on plant efficiency. Again,
values approaching the maxima should be expected under steady plant
operations.
Careful scrutiny of Table 14 for the amount of nitrogen in and out of
the unit shows that in practically all cases when carbonaceous unit
effluent is being used, apparent nitrogen increases occur within the unit.
Nitrogen imbalance is expected in biological systems but not in the
form of consistent increases. The easiest and most straightforward
explanation is to assume that some oxidation of ammonia to nitrite is
occurring in the carbonaceous unit. This is martially borne out by the
excellent balances obtained for the onlv periods, 31-40 and 41-44, in
which nitrites in the effluent were determined. An additional indication
is the frothing noted intermittently in the clarifier of the carbonaceous
unit often caused by denitrification. If this is accepted as the
explanation, then the apparent nitrogen removals reported for the carbon-
aceous unit may not be real. In addition, if this is true, then 'a
nitrogen balance across both the carbonaceous and nitrification unit
should be of interest. The last two columns of Table 14 provide this
information. The total nitrogen here is computed from the influent
values of total nitrogen for the carbonaceous unit as given in Table 8
and the percentage of carbonaceous effluent fed to the nitrification
unit is given in Table 13. The nitrogen balance in terms of percent
lost is inconsistent but varies around zero. This variation around
zero is taken as evidence that little or no change in total nitrogen
content occurs within the first two treatment units. Thus, the criteria
of effluent nitrogen oxidized definitely nlaces the upper limit on the
overall plant ability to remove nitrogen either on the basis of percentage
or absolute removals. The percentage of effluent nitrogen (roughly
equal to plant nitrogen inputs) oxidized has been discussed. This
parameter along" with the absolute amount of oxidized nitrogen produced
will be utilized to define periods of stable and unstable operations.
The first sixty days for the nitrification unit consisted of onerating
directly on the effluent from the carbonaceous unit. During this
period, the carbonaceous unit was treating only a 15 percent dilution
of a relatively weak ammoniacal liquor. Operation was not ontiraum,
however, because of low reactor temperature. The response of the
79
-------
nitrification unit to this effluent was slow but steady improvement in
the amount of nitrogen oxidized and in the percentage of influent
ammonia oxidized. The amount of ammonia removal within the unit remained
low and probably indicates that most of the nitrification is taken place
within the underloaded carbonaceous unit.
Just as increases in waste loads under treatment were being made, an
unfortunate failure of the temperature control equipment for the
carbonaceous unit took place and resulted in failure of that unit
accompanied by transfer of poorly treated waste to the nitrification
unit. This resulted in a drastic decrease in the quantity of nitrogen
oxidized by this unit and indicated impending failure. To provide the
nitrification unit with an ammonia feed during the interval required
for recovery of the carbonaceous unit, intermittent use of synthetic
feed was practiced until day 75.
The unit was returned to carbonaceous effluent feed on day 75. This
action was accompanied by a change in reactor temperature to about
90°F. During the first week of this interval, the influent ammonia
concentration increased from 600 to 1,200 mg/1 which represented the
maximum concentration of ammonia received by the unit during the entire
test. The period between days 82 and 91 was also marked by the excellent
treatment of 40 percent waste by the carbonaceous unit. The nitrifica-
tion unit responded to all these factors by producing rapidly increasing
effluent concentrations of oxidized nitrogen. During one sampling
interval, effluent oxidized nitrogen increased by almost 150 mg/1 per
day. This was the maximum observed rate of increase and may give some
indication of the response time of the unit to changes in the influent
characteristics. Unfortunately, before steady state conditions were
established, and just as improving percentages for removal of ammonia,
ammonia oxidized, and effluent nitrogen oxidized were becoming apparent,
the carbonaceous unit again became upset.
A sudden decrease in the temperature of the carbonaceous unit accompanied
by increasing loadings in the periods folloxtfing day 90 subjected the
nitrification unit to a poorer quality effluent including phenolics of
about one mg/1 for a short interval. In addition, this problem vras
accompanied by a decrease in nitrification unit temperature (96 to 86°F)
and the combination resulted in a sudden decrease in nitrification
efficiency. This unit failure was followed by a period from days 97 to
122 of unsteady operation and feed. During this period, the carbonaceous
unit again experienced problems and the unit x
-------
The decision was made, however, that the carbonaceous effluent would be
diluted prior to being applied to the nitrification unit. The purpose
of this dilution was to reduce and dampen fluctuations in the quality
of carbonaceous effluent resulting from operational changes in that
unit. Unfortunately, three days prior to the conversion (day 152)
the nitrification unit, while still on artificial feed, was subjected
to a pH of 9.9. Analyses of samples taken the following day indicated
a decrease in nitrification. However, before all of the ramifications
of the units condition were known, the unit was converted to diluted
waste. The unit did not respond and was returned to artificial feed
on day 180 without success.
Following a time of treatment disruptions resulting from mechanical
problems, the unit was again placed on a feed of diluted carbonaceous
effluent on day 216. This time the unit responded slowly and showed
a steady improvement in nitrified nitrogen. During this interval
reactor temperatures of about 90°F and pH values around 7 were
experienced. On day 249, after about two weeks of poor quality
carbonaceous effluent, the nitrification unit was placed on intermittent
synthetic feed to avoid upsetting this unit. On day 257, after improve-
ment in the carbonaceous unit, the nitrification unit began receiving
an effluent supplemented by artificial ammonia. Upon resumption of
treatment the unit apparently had no ill effects from the transition.
Oxidized nitrogen levels as well as percent ammonia oxidized and effluent
nitrogen oxidized v?ere all at or near maximum possible levels.
This period of excellent performance was followed by a period which
extended to the end of the experiment in which reactor temperatures
were low, mostly in the low to middle eighties. This period can be
subdivided into two parts based on influent feed. The first part, from
about days 260 to 310 consisted of a diluted carbonaceous effluent plus
artificial ammonia. Unit response was not satisfactory. The combination
of low reactor temperature plus a relatively poor carbonaceous effluent
resulting in high loadings of chemical oxygen demanding materials
including phenolics may have been responsible.
The second part of this period, from about day 315 to the experiment's
conclusion, utilized only diluted carbonaceous effluent without supplemen-
tal ammonia. This effluent was much improved in quality over that of
the preceding period. The nitrification unit responded well, especially
in light of the low reaction temperature, by providing several short
periods in which excellent nitrification occurred and in which 75 to 90
percent of the nitrogen was nitrified.
A major problem with the entire nitrification experiment was that condi-
tions were never stable enough for a period of sufficient length to
allow establishment of a steady state. In biological systems, variation
almost invariably leads to less than optimum performance. Good
nitrification was obtained most consistently only when the carbonaceous
unit was operating in a satisfactory manner. In addition, best nitrifi-
cation was obtained at reactor temperatures of 90 to 95°F with relatively
81
-------
poor nitrification at 80 to 85° F. Unit failures or problems resulted
mostly from carbonaceous unit failures. One failure was caused by a
high reactor pH 9.9. The optimum pH range appears to be about 6.8 to
8.2.
An attempt to outline a reaction mechanism for the nitrification unit
including an alkalinity balance computation is given in Appendix C.
DENITRIFICATION UNIT
Denitrification is the major function of the third treatment stage. As
outlined previously in Section V, denitrification is the process in
which nitrate and nitrite nitrogen is biochemically reduced to nitrogen
gas with the concurrent oxidation of organic matter. Denitrification
thus has the potential for converting potential nitrogenous contaminants
into an inert form.
The denitrification system was placed on line January 29, 1970, and
initially received one (1) gallon per minute of nitrification unit
effluent. This flow represented a reaction time of approximately 8
hours. Detailed surveillance of the influent and effluent began with
the first averaging period in February which began for this unit on the
third because of the two 24-hour detention periods in the preceding
treatment stages.
Tables 15 and 16 provide summaries of the operating conditions and
operating results for the denitrification unit. More detailed information
may be found in the Appendix. Being the last of the three units, the
denitrification reactor was subjected to all of the fluctuations either
encountered or resulting from the previous treatment stages.
Table 15 gives the summary of the major operational parameters measured
routinely during the test of the denitrification unit. Essentially the
only control exercised over this unit was through the amount of
reducing agent added. During roughly the first one-fifth of the
experiment, sucrose sugar was used while in the remainder of the experiment,
molasses was used. The amounts of these materials added are given for
each period in the first two columns. As with all biological processes,
temperature and pH are important, but no control over these parameters
was exercised in the denitrification unit. Temperature within the reactor
varied from a low of 71 to a high of 93°F. This variation would be
expected to influence greatly the rate of denitrification. The pH
and alkalinity increase as a result of the overall denitrification
process. Values of pH as high as 9.2 and alkalinity increases of up to
almost 1,000 mg/1 as CaC03 were experienced. Dissolved oxygen concentra-
tions approaching one mg/1 were encountered during the experiment without
apparent disruption of denitrification.
82
-------
The denitrification process depends upon the availability of organisms
capable to utilizing oxidized nitrogen in their metabolic processes.
The use of the Imhoff Cone to measure the concentration of these organisms
in this unit was less than adequate. First, the Imhoff Cone measurement
depends upon sedimentation of the organisms and denitrifying sludges,
instead of settling, often tend to float because of entrapment of
released nitrogen gas. An additional complication resulted because,
without doubt, some biological growth took place because oxygen entered
the system through the surface of the stirred reactor. Despite these
complications, there is some evidence from the data to suggest that
Imhoff Cone readings do correlate with the- degree of denitrification.
Limited suspended solids measurements indicate low biological levels.
No routine blowdown from this unit was made. Slowdown actually occurred
through the discharge of a turbid effluent resulting from poor sedimenta-
tion of this particular sludge. Low Seechi Disk readings confirm the
turbid nature of the effluent.
The operational problems encountered by this unit included, in addition
to mechanical problems such as influent flow and sludge return disruptions,
a bulking sludge on occasion. The bulking nature of the sludge made
mandatory a surface skimming device to collect sludge from the
sedimentation compartment for return to the reactor.
The major operational function of the denitrification unit is to reduce
the nitrite and nitrate formed in the preceding treatment units to
nitrogen gas using an added reducing agent. Obviously, the nitrite and
nitrate concentrations in the influent and effluent are important
operational parameters and are tabulated in Table 16. Since one of the
functions of the three-stage plant was the overall removal of nitrogenous
matter, ammonia and total nitrogen concentrations are also given.
The organic content of the effluent is a most important operational
factor. The origin of this material may be either the residual not
removed in the two preceding treatment units or that intentionally added
as either sugar or molasses. These quantities are entered in Table 16
in terms of chemical oxygen demand. To assist in judging the efficiency
of the treatment unit, percent losses or removals of ammonia, oxidized
nitrogen, total nitrogen, and chemical oxygen demand are also listed.
The removal of ammonia is not a function of this unit and losses of
this component were not expected to be large. Small losses may be
accounted for by incorporation into the sludge. Actually, as can be
seen from Table 16, in many of the periods ammonia increases within the
unit are noted. Since ammonia removal is one of the primary objectives
of the treatment scheme, any increase in ammonia is undesirable. Several
possible reasons exist for this observation. The worst possible case
would be the reconversion of nitrite and nitrate by denitrification into
ammonia rather than nitrogen gas and organisms are known which are capable
of this. Unfortunately, if this were the case, nothing would be
accomplished by the nitrification and denitrification treatment steps.
83
-------
The non-consistent nature of the gains and losses in ammonia cast some
doubt on this explanation. More careful examination of the operating
ponditions existing during periods of gains and losses of ammonia pointed
out an interesting correlation. With only a very few exceptions, ammonia
gains are noted only when artificial ammonia is being added to the
nitrification unit and only losses occur when the nitrification unit is
entirely on waste feed. The best explanation for this observation appears
to be purely an operational one rather than biological. During times
of artificial ammonia additions to the nitrification unit, slugs of
ammonia sulfate were added once per day. This meant that ammonia
Concentration in the effluent varied with time. In addition, the
amount in the effluent from the denitrification unit x^ould also vary.
Since samples for ammonia were collected simply by grab techniques, the
observed results could easily be obtained. However, when all units are
treating waste waters, there is no slug effect as all systems are running
gmoothly and concentrations of constituents do not change rapidly. At
any rate, during periods when waste is being treated and since this is
the time of maximum importance, small losses of ammonia, possibly
ranging to 10 or 20 percent, might be expected within the denitrification
stage.
The major change expected within this unit is the decrease in the
content of oxidized nitrogen. Oxidized nitrogen losses of greater than
95 percent occurred with some regularity during the test. Considering
the lack of consistency in the preceding treatment steps, these results
indicate that the denitrification unit is capable of performing its
intended function.
The loss of total nitrogen in the unit is not an effective measure of
the efficiency of the denitrification treatment unit alone, but rather
pf the nitrification and denitrification unit combined. For the most
part, only the nitrification unit can treat ammonia and the only
nitrogenous materials capable of sizable removals in the denitrification
tin it are oxidized forms. Thus, only with both units operating at peak
efficiency will good overall removals of nitrogen be obtained. Unfor-
tunately, the nitrification unit seldom oxidized more than 75 percent
pf its effluent nitrogen. This means that for most of the time at least
?5 percent of the nitrogen passing on to the denitrification unit was
tmoxidized. For practical purposes, 75 percent removal of total
nitrogen is an upper limit even with 100 percent effectiveness of the
denitrification stage. Actual losses approaching 70 percent x^ere
Pleasured for some averaging periods.
The reduction of oxidized nitrogen by the use of artificial reductants
Such as sugar or molasses needs careful control. Only with control
can the proper stoichiometric quantity be added that will supply just
enough reductant to reduce the oxidized nitrogen content adequately
without providing an excess that will not be oxidized and thus pass
84
-------
TABLE 161. OPERATING RESULTS. DENITRIFICATION UNIT
J
3-7
8-15
16-23
24-31
32-41
42-45
46-50
51-57
58-59
60-62
fcl 7 1
D J / J
76-78
79-83
84-86
87-90
91-93
94-97
QD 1 O*3
yt> i*. j
124-131
132-138
139-145.
146-152
153-159
160-166
167-173
174-180
181-187
168T194
195-202
203-216
217-222
223-229
230-236
237-243
244-250
251-257
258-264
265-271
272-278
279-285
286-292
293-299
300- 306
307-313
314-320 .
321-327
328-334
335-341
342-348
349-352
INFLUENT
z
190
220
170
160
120
180
230
220
220
310
190
710
610
740
550
Z
1
(U
•ft
z
40
48
56
61
77
69
69
76
110
127
N T E
z
0)
Nltrat
40
53
71
70
89
87
91
108
87
114
DMT
230 103
215
185
344
396
660 192
T N T F B
L B 1 C. I
210 , 3
50
120
50
67
156
230
182
115
348
441
214
;M T T
H ,L J
4
64
145
200
CONCENTRATIONS, mg/1
"S
N
V Z
S c
X «l
O 00
4J -r<
80
100
130
130
160
150
160
180
200
240
TT F
X I*
330
400
300
690
840
410
TF K
& r
7
130
300
430
z
^ 1
-* c
• 00
4J U
r =
270
320
300
290
280
330
390
400
420
550
NT 1
J. L
520
1110
910
1430
1390
1070
TIT
U
220
180
420
480
COD, as 02
e
o
.H
•J u
n c
11 01
itrifli
Efflui
BE
Ic F
D &
SP r
fc t.
220
300
c
HI
IncreoH
Added
380
210
210
210
300
380
380
380
380
380
01? i
e f
330
330
260
330
330
330
F*
A
660
660
660
660
Total
-
-
-
-
-
-
-
-
880
960
EFFLUENT
Z
id
•H
C
170
210
170
140
100
150
170
210
180
290
140
630
980
740
530
890
410
120
180
110
z
i
Lf
U
*4
Z
23
2
33
8
17
0
0
0
0
0
11
130
92
260
410
190
0
13
21
100
INTERMITTENT USE OF ARTIFICI
230
33O
1OOO
200
120
70
149
135
46
25
49
41
112
138
40
26
37
37
260 490 340
270
90
50
90
80
600
1090
250
210
150
350
490
90
80
80
MAJOR FLOW PR
190
330
38O
250
240
101
210
241
257
227
103
176
188
221
288
200
390
430
480
510
390
720
810
730
750
400
570
650
620
650
660
660
660
660
660
660
1000
1010
1150
750
74O
740
0 B t E M S
660
660
660
660
660
1060
1230
1310
1280
1310
200
310
960
360
170
110
14
8
0
0
0
13
E N C 0 U N
150
300
370
250
170
12
7
31
70
70
CONCENTRATIONS, mg/1
z
V
z
24
2
40
11
20
1
1
2
1
1
Am.
M
82
110
58
260
330
200
A M M
0
17
69
91
A L t
15
6
0
0
0
T E R
10
6
25
74
103
«
S
ll
00
•-* o
CO Id
82
50
5
70
20
40
1
1
2
1
1
M/*l **
U N
90
240
150
520
740
390
ONI
0
30
90
190
M M (
30
10
0
0
0
30
E D
22
10
60
140
170
INTERMITTENT USE OF ARTIFICIAL AMMONI
50
130
150
510
400
110
70
110
. .80
"190
50
140
360
470
326
267
152
0
0
0
154
263
210
140
222
209
62
127
366
335
189
58
83
128
201
197
204
131
243
231
112
171
690
600
340
60
80
130
350
460
410
270
460
440
170
300
740
730
490
570
48O
240
420
570
490
460
510
580
530
770
510
500
430
280
300
360
430
420
440
360
450
470
360
340
1000
1000
10OO
1000
850
660
660
900
1000
1000
1000
1000
850
1000
1510
1500
1430
1280
1350
1020
109O
1320
1440
1360
1450
1470
1210
1340
90
170
140
530
470
150
100
130
80
160
50
130
470
460
86
4
18
0
0
0
38
29
19
0
26
26
1
0
105
7
16
0
0
29
32
32
15
0
27
31
2
0
190
10
30
0
0
30
70
60
30
0
50
60
3
0
z
t
c
OJ
00
0
k<
«J
o
H
270
240
270
180
160
190
-
240
210
III n
A A
900
1190
-
1330
-
A At
420
170
290
320
N I A
260
350
-
380
190
150
200
350
600
440
720
-------
through the plant and degrade effluent quality. Reductants, as
measured by the chemical oxygen demand and mentioned previously, are
either residual organlcs resisting removal in the previous treatment
steps or artificial additions of sugar or molasses. The losses or
utilization of the total chemical oxygen demand is given as a percentage
of total input to the system in Table 16. These values for the most
part vary between 40 and 60 percent. The removals are low in part,
because of the refractory nature of much of the COD. The utilization
of added COD materials which are not refractory is given in the last
column. Percentage losses for COD on this basis approaches 90 percent
in some tests.
The most critical aspect of the operation of the denitrification unit
is the determination of the amount of reductant necessary to result in
removal of the oxidized nitrogen without having an excess. This amount
of reductant can be estimated in several ways. Stoichiometrically, the
amount can be computed based upon assumed oxidation-reduction reactions
and measured concentrations of nitrite and nitrate. These computations
for the last three months of the test are given in Table 17. The
concentrations of oxidants, nitrite and nitrate and reductants as
measured by chemical oxygen demand both in and out of the unit are
reproduced from Table 16. The following derivations allow the
conversion from concentration units to milliequivalents per liter (meq/1)
(1) Nitrite to nitrogen gas
Thus,
2NO~ + 8H+ + 6e
meq/1 (NO ') - _3 C
14
where the electron (e"~) change per mole or equivalents per mole of nitrite
equals 3 and there are 14 grams of nitrite-nitrogen per gram molecule.
C - is the concentration of nitrite in mg/1 as nitrogen.
(2) Nitrate to nitrogen gas
2NO~ + 12H+ + lOe"
Thus
meq/1 (NO ~) - _5 CMn-
14 N°3
86
-------
TABLE 17;
DENITRIFICATION - STOICHIOMETRIC COMPUTATION
Period
279-285
286-292
293-299
300-306
307-313
314-320
321-327
328-334
335-341
342-348
349-352
OXIDANTS
Nitrite
In
mg/1
0
0
0
154
263
210
140
222
209
62
127
Out
mg/1
0
0
0
38
29
19
0
26
26
1
0
Change
mg/1
0
0
0
116
234
191
140
196
183
61
127
meq/1
0
0
0
251
50
41
30
42
39
13
27
Nitrate
In
mg/1
58
83
128
201
197
204
131
243
231
112
171
Out
mg/1
0
0
29
32
32
15
0
27
31
2
0
Change
mg/1
58
83
99
169
165
189
131
216
200
110
171
meq/1
21
30
35
60
59
68.
47
77
71
39
61
Total
Change
meq/1
21
30
35
85
109
109
77
119
110
52
88
REDUCTANTS
Chemical Oxygen Demand
In
mg/1
1280
1350
1020
1090
1320
1440
1360
1450
1470
1210
1340
Out
mg/1
1070
1020
640
500
580
580
730
630
690
670
660
Change
mg/1
210
330
380
590
740
860
630
820
780
540
680
meq/1
26
41
48
74
93
108
79
102
98
68
85
Error
Ox .-Red.
meq/1
- 5
-11
-13
11
16
1
- 2
17
12
-16
3
%
of
Reductants
19
27
27
15
17
1
3
17
12
24
4
oo
-J
-------
(3) Chemical Oxygen demand
The COD reaction in terms of oxygen can be
written as
Thus,
meq/1 (COD) - C
COD
Using these equations, the change in milliequivalents per liter of
nitrite, nitrate, and chemical oxygen demand between the influent and
effluent of the unit were computed. Since, on an equivalent basis,
oxidations must equal reductions, the difference or error should be zero.
Actual errors, for those averaging periods shown in Table 17, are as
high as 17 meq/1 and up to almost 30 percent. Computations of the same
parameters for less uniform operating periods show even larger errors.
The fact that the computed errors show excesses of oxidants during
some periods and almost equal excesses of reductants during others
tends to indicate that no consistent error was incorporated into the
reaction theory. In other words, the reactions proposed fit the
experimental data as well as could be expected. The errors may well
result simply from the unsteady nature of the operation and the use of
grab samples. In addition, the changing efficiencies in the separation
of the organisms in the sedimentation tank due to sludge bulking and
other factors can have a large effect on the chemical oxygen demand of
the effluent and in turn on the redox balance.
All in all, the theory proposed agrees with that found in the laboratory
experiments and that proposed by others, and this data tends to varify
its validity. On this basis, it is assumed that the major reduction
reactions occurring within the denitrification unit are the formation
of nitrogen gas from nitrite and nitrate and that the simultaneous
oxidation involves converting organic carbon to carbon dioxide. The
latter reaction can be monitored easily through the use of chemical
oxygen demand measurements. The dosage of organic reducing agent needed
for denitrification can then be computed in terms of COD for various
nitrite and nitrate concentrations by the following equation:
n *c fi( c 4- p ^ i
"COD °44 ^NO, - 14 LNO, -'
£ O
where D n s stoichiometric COD dosage in mg/1,
COD
CNO - * nitrite concentration in mg/1 as N, and
CNQ _ » nitrate concentration in mg/1 as N.
88
-------
This stoichiometric computation may be used as a first approximation
of the required amount of reducing agent to convert the oxidized
nitrogen forms to nitrogen gas. However, this computation assumes
that the reaction will go to completion without excess reagent being
present. Data, as given on Table 16, indicates that during the best
period of operation, 91 percent of the added chemical oxygen demand
was oxidized while 97 percent of the oxidized nitrogen was lost.
Several other tests indicate that 90 percent of COD and 95 percent
loss of nitrogen should be possible with proper analytical and operational
controls. The total amount of COD necessary in terms of mg/1, TCQ_, then
would equal
TCOD " 8'9 (14 CN02 - + 14
The concentration of COD in the effluent would be the residual
passing through the nitrification unit plus an amount approximately
equal to 10 percent of TQQQ. The effluent would also be expected to
contain about 5 percent of the oxidized nitrogen in the influent to
the denitrification unit.
89
-------
SPECIAL STUDIES
During the course of this investigation, several special projects were
conducted to enhance the understanding of aramoniacal liquor treatment,
to extend treatment capabilities, to investigate use of supplementary
treatment steps, and to reduce treatment costs. These studies of most
interest were concerned with the carbonaceous treatment unit and develop-
ment of alternate methods of denitrification.
CARBONACEOUS UNIT
The treatment of ammoniacal liquors for removal of carbonaceous materials
has been repeatedly demonstrated. However, the treatment has only been
accomplished with considerable difficulty and with less than optimum
results in some instances. For example, the waste must be diluted prior
to treatment and thiocyanate has been difficult to remove.
Near the end of the experimental phase of this project, a pretreatment
step was proposed that reportedly made the waste more amenable to bio-
logical treatment. This proposal was made by International Hydronics
Corporation, and reference is made to this under the authors' names, W.
G. Cousins and A. B. Mindler, in Section V, Essentially this pretreat-
ment process consists of free and fixed ammonia distillation at pH 11,
followed by addition of spent pickle liquor for both neutralization and
coagulation. Following sedimentation, the waste is reported to be more
easily treated.
The laboratory modification of the proposed pretreatment step was to
treat a batch of excess ammoniacal liquor with lime to a pH of 11 and
to heat this mixture to approximately 93°C. Aeration was then applied
to strip ammonia to any desired level. After cooling, synthetic spent
pickle liquor consisting of one percent free hydrochloric acid and 6
percent ferrous iron was added to chemically coagulate the liquor and
to reduce the pH of the waste to about 9. After sedimentation, the waste
was ready for treatment in the experimental unit!. Typical percentage
reductions in some of the major components as a tesult of the treatment
are given in Table 18 for an excess ammoniacal liquor from a coke
plant in the Pittsburgh, Pennsylvania, area. As can be seen, this treat-
ment procedure results in a considerable change in some of the major
waste constituents, especially cyanide.
91
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TABLE 18: PRETREATMENT OF EXCESS AMMONIACAL LIQUOR, PERCENT REMOVALS
Aeration Coagulation only, Aeration and
Constituent only no aeration coagulation
Chemical oxygen
Thiosulfate
Sulfide
Organic carbon
Phenolics
Ammonia
Cyanide
Thiocyanate
25
25
20
20
15
—
80
0
20
20
10
10
10
0
90
0
30
35
30
25
20
—
90
0
The treatability of this waste x
-------
TABLE 19: BIOLOGICAL REMOVALS FROM PRETREATED ,WASTE
Pretreatment Procedure
Aeration & Coagulation Coagulation only
Cone., mg/1 percent Conc.^mgA Percent
Constituent Inf. Eff. Removal Inf. Eff. Removal
Ammonia, N.
Phenolics, phenol
Organic carbon, C
Thiocyanate, SCN
Chemical oxygen demand, 00
500
1700
2000
960
7100
-
2
700
920
2800
-
99+
65
5
60
4000
1400
1900
1100
6800
-
3
800
1100
2900
-
99+
60
0
55
The difference betx
-------
consisted of a 10 percent dilution of excess amrnoniacal liquor whose
pH had been adjusted to about 7 and to which phosphate had been added.
At this dilution, the influent contained about 140 mg/1 of phenolics
and 105 mg/1 of thiocyanate.
Operating with an aeration time of 24 hours, after five days over 90
percent removal of phenolics was noted but no thiocyanate was removed.
Under past operating criteria, waste strength would have been increased
based on phenolics removal; but since in this instance thiocyanate removal
was paramount, influent loading was maintained. It was not until day 12
that thiocyanate removal was noted. On that day, about 50 percent removal
was noted, and on the following day over 99 percent was lost. The influ-
ent waste concentration was then slowly increased in steps with careful
monitoring of the effluent for phenolics and thiocvanate. After each
incremental increase, both phenolics and thiocyanate would normally be
present in the effluent in low concentrations with phenolics disappear-
ing before the thiocyanate. After a few failures of the system, it was
determined that with this particular ammoniacal liquor, only about 25
percent x^aste could be treated in the test unit and obtain consistent
removals of thiocyanate of better than 90 percent. The maximum concen-
tration of thiocyanate treated under these conditions was about 300 mg/1
with effluent levels of about 10 mg/1.
After the conclusion was drawn that the limiting concentration of this
excess ammoniacal liquor that could be processed in the test unit for
thiocyanate removal was 25 percent, the unit was converted to coagulated
waste feed. The use of pretreated waste allowed the use of 50 percent
waste concentrations to be utilized by the unit, and to maintain thiocyanate
removals. Thiocyanate levels as high as 525 mg/1 were reduced to 20 mg/1
during periods of optimum operations.
In summary, for laboratory units utilizing a 24-hour aeration time and
room temperatures, treatment for phenolics removal was possible at a
maximum waste concentration of 60 percent. This waste, with pretreat-
ment, could be treated for phenolics removal without dilution. Thiocyanate
removal frpm this same waste was only possible at a waste concentration
of 25 percent and with pretreatment, this maximum was increased to 50
percent.
Chemical studies of the reaction products of the thiocyanate sulfur indicates
that about one-half is converted to sulfate with no sulfide, sulfite, or
thiosulfate. The exact fate of the other half was not determined but
elemental sulfur is suspected.
DENITRIFICATIQN UNIT
Sizeable quantities of reducing agent are needed to satisfy the demands
of a well-nitrified ammoniacal liquor in the denitrification process.
The use of either sugar or molasses for this purpose is expensive and
alternatives were sought. Among the alternatives given consideration
were the use of ferrous iron, the raw waste itself, and municipal sewage.
94
-------
The use of ferrous iron, a well-known chemical reducing agent, for the
treatment of coke plant wastes appears to be an optimum solution consider-
ing that the steel industry also produces sizeable quantities of wastes
containing ferrous iron. A report by Gunderloy, e£ al. (65) proposes
the use of ferrous iron specifically for denitrification. Numerous
attempts by the laboratory staff to reproduce the results reported or to
denitrify wastes were unsuccessful as most all of the oxidized nitrogen
reduced could be accounted for as nitrite or ammonia. After consider-
able testing, this alternative was abandoned. '
Another potential alternative for a source of reducing agent was the
waste itself. The wastes capacity for reduction is measured by its
chemical oxygen demand. Several operational schemes are possible in
which great savings in air requirements and neutralizing chemicals can
accrue if raw waste can be treated using nitrite and nitrate as oxidizing
agents. Unfortunately, denitrification could not be initiated using
atranoniacal liquor as the reductant even though much care and patience
was exercised.
A last possibility considered was the use of the nitrified effluent from
the second stage of the treatment scheme to oxidize or treat municipal
wastes. Many (see Section V) have shown that oxidized nitrogen can be
used as a substitute for some of the oxygen required to satisfy the car-
bonaceous oxygen demand of domestic wastes. As an example of the po-
tential of this process, let it be assumed that the excess ammoniacal
liquor has an ammonia concentration of 4000 mg/1. In addition, assume
that one-half of the ammonia is nitrified to nitrite and the other to
nitrate. According to equations developed in Section VIII, this amount
of nitrite and nitrate will equal about 1150 milliequivalents per liter
for the reaction to nitrogen gas. The non-settleable chemical oxygen
demand of a municipal waste is estimated to be about 200 mg/1. In terms
of milliequivalents per liter, this is 25. This means that for a stoichio-
metric reaction the flow of municipal waste would need to be almost 50
times the flow of ammoniacal liquor. In other words, 100,000 gallons of
a well-nitrified ammoniacal liquor could satisfy the entire carbonaceous
oxygen demand of 5 million gallons of domestic sewage. The savings in
denitrification cost to the coke plant and aeration capacity to the
municipal treatment plant are obvious.
95
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SECTION X
COST ESTIMATES
In this Section estimates of the capital and operating costs of a
biological system designed to remove nearly all of the phenol and
ammonia from excess ammonia liquor are developed. Other contaminates
such as C.O.U., cyanide and thiocyanate will have smaller percentage
removals. The costs developed here are not intended as firm estimates
for an actual treatment system. Rather, they are the most probable
costs based on available but incomplete technology. The basis for
the estimates is a scale-up of the pilot system used in this study.
As described in previous sections, numerous problems were encountered
during the operation of this system. Many of these problems were
solved during the course of the study but others went unresolved.
Additional development work will be required to define the unanswered
questions before the system can be considered for full scale application.
This development work may have a substantial impact on the actual costs.
For this reason, the following estimates should be used only for
evaluating the need and potential return of further development work.
A coke plant producing 33,000 tons per month (TPH) was selected as
the basis for the cost evaluation. This size system is representative
of a large number of existing coke plants in this country. With only
minor adjustments, the costs developed here should be applicable to
many existing facilities. In those cases where scale-up or scale-dox^n
is necessary, it is recommended that the logarithmic method frequently
used in chemical engineering be employed to adjust the capital cost.
This method is expressed as follows:
Cn = rXCe
where Cn is the new plant cost, Ce is the estimated cost from this
report, r is the ratio of new waste volume to 40,000 gpd, and x is
the scaling factor. A value for x of 0.65 is suggested.
The production of 33,000 TPH coke from coal with 5 percent moisture
will result in the discharge of approximately 40,000 gallons per day
(gpd) of excess ammonia liquor. Typically this waste will contain
6000 ppra (2000 Ibs/day) C.O.D. and 4000 ppm (1350 Ibs/day) NH--N.
It is assumed that this waste will be diluted to 50 percent strength
(80,000 gpd) before treatment in the carbonaceous removal unit. The
carbonaceous removal unit effluent will then be diluted to 25 percent
strength (320,000 gpd) prior to treatment in the nitrification and
denitrification units. At these dilutions 80 percent C.O.D. removal
and 95 percent removal of NH3-N is expected. The capital cost of
the three stage treatment system designed to handle this waste volume
is estimated at $995,000. This cost is for a battery limits plant
located on a developed site. A breakdown of the estimate is given in
Table 20.
97
-------
TABLE 20: CAPITAL COST E.A.L. BIOLOGIC AT, TREATMENT
I. CARBONACEOUS REMOVAL UNIT
E.A.L. Storage Tank
Aeration Tank
Clarifier
Surface Aerator
Transfer Pumps (2)
Sludge Recycle Pumps (2)
Phosphoric Acid Feed
Antifoam Feed
Sludge Drying Bed
Structural Steel
Piping and Valves
Electrical and Instrumentation
II. NITRIFICATION UNIT
Aeration Tank
Clarifier
Surface Aerators (2)
Sludge Recycle Pumps (2)
Sodium Carbonate & Lime Ai
Structural Steel
Piping and Valves
Electrical and Instrument.
III. DENITRIFICATION UNIT
Mix Tank
Air Flotation Tank
Mixers (2)
Sludge Recycle Pumps
Molasses Addition
Structural Steel
Piping and Valves
Electrical and Instrumentation
DESIGN
CRITERIA
48 hr. det.
24 hr. det.
350 gpd/ft2
2.5 Ibs. 0,/hn hr
2
1 1/ra gal E.A.L.
67 ml/m gal E.A.L.
:tion
Sub Total
24 hr. det.
350 gpd/ft2
2.5 Ib. 02/hp hr.
200 gpra
idition
it ion
Sub Total
8 hr. det.
700 gpd/ft2
0.1 hp/m gal.
it ion
Sub Total
:OTAL DIRECT COSTS
INDIRECT COSTS
?OTAL PROJECT COST
UNIT
SIZE
80,000 gal
80,000
20 ft dia.
40 hp
30 gpm
60 gpm
10 gpd
1 gpd
320,000 gal
35 ft dia.
45 lip
110,000 gal
25 ft. dia
6 hp
200 gpm
COST
$ 21,000.
27,000
30,000
11,000
2,000
,4,000
10,000
10, '000
15,000
12,000
35,000
50,000
$227,000
$ 73,000
53,000
24,000
6,000
30,000
15,000
40,000
50,000
$296,000
$ 36,000
53,000
10,000
6,000
15,000
15,000
40,000
50,000
$225,000
$748,900
$247,000
$995,000
98
-------
The costs presented in Table 20 are based on scale-up of the pilot
plant described in Section VI. To solve some of the operating problems
encountered during the pilot study, four modifications to the original
design were made. Excess ammonia liquor storage was increased from 24
hours to 48 hours to provide more cooling and equalization. The system
was designed for gravity flow between treatment modules to eliminate
the transfer stations. Caustic addition to the nitrification unit was
replaced with separate systems for the continuous addition of lime and
soda ash. And, the denitrification unit final clarifier was converted
to an air flotation system to eliminate biological solids losses from
sludge bulking.
The operating cost of the system is estimated at $230,500 per year.
This estimate reflects current steel industry costs for materials,
utilities, and labor. A breakdown is given in Table 21. For a
33,000 TPM plant, the unit treatment cost is $15.78/1000 gallons.
In terms of production, this is an increase of $0.58/net ton coke.
If it is assumed that production cost above initial coal cost is
$7.00 per net ton, biological waste treatment would represent a cost
increase of about 8.7 percent.
In evaluating the operating costs, two items warrant further dis-
cussion. First, it was assumed that hydrated lime and sodium carbonate
would be used in the nitrification unit for pH control and a source of
inorganic carbon. There are a number of compounds or combinations of
compounds that could be used to supply these requirements. A cost
comparison of four possible chemical systems is given in Table 22.
As shown, the limestone system is the most economical from a chemical
cost standpoint. The requirements for handling larger tonnages of
limestone and increased amounts of waste sludge resulting from unreacted
limestone outweigh the cost advantage, however. For this reason, the
sodium carbonate-hydrated lime system was selected as the most practical
method of pH control and source of inorganic carbon.
The second item is the use of molasses as a source of organic carbon
in the denitrification unit. This carbon requirement could be
supplied with a variety of materials. Almost any organic compound
which is water soluble and biodegradable could be used. The economics
of several materials were evaluated during the study. A summary of
the evaluation is given in Table 23. Molasses is the least expensive
of the materials considered. For this reason, it was used for the
cost evaluation. In some parts of the country, however, molasses may
not be available. In these areas organic carbon costs should be
developed around methanol. This is the most economical alternate
and a material that has been reported successful in denitrification by
numerous investigators.
99
-------
TABLE 21: OPERATING COST BIOLOGICAL TREATMENT
Operation: 3 turns/day, 365 days/year
Waste Volume: 40,000 gpd E.A.L.
Fixed Investment: $995,000
DIRECT COSTS UNITS/YR. $/UNIT $/YR.
•y '
Materials:
Molasses 700 Tons 24 17,000
Sodium Carbonate 600 Tons 50 30,000
Hydrated Lime 720 Tons 20 14,400
Phosphoric Acid (75%) 20 Tons 226 4,500
Tributyl Phosphate (100%) 1.18 Tons 1170 1,380
Utilities:
Steam 55,000 mm Ibs. $ 0.75 41,000
Water 100 mm gals. 20.00 2,000
Electricity 1.10 mm kwh 0.01 11,000
INDIRECT COSTS
Operating Labor 4 man 15,000 60,000
Maintenance Labor and Material 5% fixed cost 49,220
Total Operating Cost $230,500
(Excluding Interest and Depreciation)
Unit Operating Costs: $15.78/1000 gala. E.A.L.
$0.58/Ton Coke
100
-------
^
Waste Volume: 40,000 gpd E.A.L.
Ammonia - Nitrogen: 4000 ppm (1350#/day)
MI1S/YR._ I/UNIT
*
Limestone Only
Crushed Limestone 3070 Tons 12 $ 36,800
Soda Ash Only
Granular Sodium Carbonate 1630 Tons 50 $ 81,000
Soda Ash and Caustic
Granular Sodium Carbonate 600 Tons 50 30,000
Liquid (50%) Sodium Hydroxide
1550 Tons 50 77,500
TOTAL $225,300
Soda Ash and Hydrated Lime
Granular Sodium Carbonate 600 Tons 50 30,000
Pox^dered Calcium Hydroxide 720 Tons 20 l^'J^L
TOTAL $ 44,400
,101
-------
TABLE 23: COST COMPARISON OF ORGANICS FOR DENITRIFICATION
Waste Volume: 40,000 gpd E.A.L.
Ammonia - Nitrogen: 4000 ppm (1350#/day)
THEORETICAL^
REQUIREMENTS
UNITS/YR. $/UNIT
$/YR.
Sucrose 2.59
Formaldehyde 2.59
Methylethylketone (MEK) 1.'24
Acetone 1.30
Methanol 1.90
Molasses 2.85
640 Tons
640 Tons
305 Tons
320 Tons
468 Tons
700 Tons
220
216
210
118
82
24
141,000
136,000
64,000
38,000
38,000
17,000
ft
Assuming 50% as nitrate and 50% as nitrite.
It is apparent from the estimates developed above that the biggest
percentage of the cost for biological treatment is ammonia removal.
Seventy percent of the capital cost and 80 percent of the operating
cost can be directly attributed to nitrification and denitrification.
The phenol removal system represents only 30 percent of the capital
and 20 percent of the operating costs.
102
-------
SECTION XI
ACKNOWLEDGEMENTS
The laboratory and field studies reported herein were carried out
by representatives of Armco Environmental Engineering and the Water
Resources Fellowship at Carnegie - Mellon University.
The staff of the Water Resources Fellowship sponsored by the American
Iron and Steel Institute are recognized for their very important role
in performing laboratory studies and evaluating pilot plant data.
Special recognition is given to Dr. William R. Samples formerly Senior
Fellow and Head of the Water Resources Fellowship, for his generous
assistance without which this project could not have been completed.
Mr. J. E. Barker and Mr. R. J. Thompson of Armco Environmental
Engineering are recognized for their contributions in directing and
coordinating the research and development effort on the project.
Mr. William Chadick and other representatives of the Houston Works of
Armco Steel Corporation are recognized for their contributions and
cooperation during the course of the study.
The partial financial support of the study by the American Iron and
Steel Institute and the EnvironmentaLProtection Agency is hereby
acknowledged.
103
-------
REFERENCES
— -• --F -.-•-—I•- IIBII -MT« _!• - , f
1. "Reducing Phenol Wastes from Coke Plants", Compiled by the Steel
Industry Action Committee of the Ohio River Valley Sanitation
Commission, Cincinnati, Ohio, January, 1953.
2. Barnes, Thomas H, Albert 0. Hoffman, and H. W. Lovnie, Jr.,
Evaluation of Process Alternatives to Improve Control of Air
Pollution from Production of Coke", Battelle Memorial Institute,
Columbus, Ohio, January 31, 1970.
3. Black, H. H., G. N. McDermott, C. Henderson, W. A. Moore, and H. R.
Pahren, "Industrial Waste Guide - byproduct Coke," Journal of the
Water Pollution Control Federation, 1956, 494-527.
4. Samples, William R., "Fate of Phenolics in Coke Quenching", Mellon
Institute Report, Carnegie-Mellon University, Pittsburgh, Pa., 22
July 1969.
5. Samples, William R., Unpublished Data, Mellon Institute, Carnegie-
Mellon University, Pittsburgh, Pa.
6. Rudolf's, Willem, Industrial Wastes. Reinhold Publishing Corporation,
New York, 1953.
7. Renkin, W. 0., "Ammoniacal Liquor Clarification Process", Communica-
tion to Water Resources Fellowship, Mellon Institute, July 25, 1949.
8. "Phenol Wastes Treatment by Chemical Oxidation", Compiled by The
Steel Industry Action Committee of the Ohio River Valley Water
Sanitation Commission, 1951.
9. Rhodes, E. 0., "German Low-Teranerature Coal-Tar Industry", Informa-
tion Circular 7490, U.S. Dept. of the Interior, Bureau of Mines,
February, 1949.
10. Blackburn, W. H., "The Effluent Problem of the Gas and Coking
Industries", J.Institute of Sex* a Re Purification, 199-207 (1958).
11. Ackeroyd, B. A. and G. W. J. Bradley, "Effluent Purification at the
Avenue Carbonization and Chemical Plant of the National Coal Board",
Air and Water Pollution in the Steel Industry, The Iron and Steel
Institute, London, 1958.
12. Arthur D. Little, Inc., "A Study of Coke-Oven Ammonia", (AISI),
March 9, 1961.
105
-------
13. Siewers, H. et_ ai., "Process for Destroying Ammonia Contained in
Water Resulting from the Operation of Coke Ovens", U.S. Patent
3,540,189, November 17, 1970.
14. Private Communication ("lichael Perch) September 27, 1966.
15. Private Communication (R. E. Iluder) October 27, 1966.
16. Rosenblatt, E. ?. and J. 0. Cohn, To Baher Co., Inc., "Dissociation
of Ammonia", U.S. Patent 2,601,221.
17. Samples, W. R., "Lira!tins the Output of Ammonia from Coke Plants
and Steel Mills", Mellon Institute, Pittsburgh, Pa.
18. Hcliichael, F. C., "Ammonia Decomposition and Oxidation", Mellon
Institute, Pittsburgh, Pa., February 1969.
19. Vigani, F., "A Literature Review of Ammonia Synthesis and Decomposi-
tion by Catalysts of Iron", Mellon Institute, Pittsburgh, Pa.,
February 1969.
20. Temkin, il. I. and Pyzhev, V., ACTA Physiochem., USSR, 12, 327 (1940).
21. Emmett, P. II. and Love, K. S., J. Araer. Chem. Soc., 63, 3297 (1941).
"The Catalytic Decomposition of Ammonia Over Synthetic Ammonia
Catalysts".
22. White, A. II. and Melville, W. , "The Decomposition of Ammonia at High
Temperatures", J. Amer. Chem. Soc., 27, April 1905, p. 373-336.
23. Thomas, Charles L., "Catalytic Processes and Proven Catalysis".
24. British Patent 746,697, February 17, 1954, "Process for Destroying
or Preventing the Formation of Ammonia During the Coking of Coal".
25. Hill, William H., "Recovery of Ammonia, Cyanogen, Pyridine, and Other
Nitrogenous Compounds from Industrial Oases, "Mellon Institute,
Pittsburgh, Pa. (1942).
26. Wilson, Philip J. and Wells, J. H., "Coal, Coke and Coal Chemicals",
McGraw-Hill Book Company, Mew York, 1950.
27. Dean, R. B., "Nitrogen Removal from Wastewaters", Paner No. 5
"Removal of Ammonia by Selective Ion Exchange", F.W.Q.A. , Cincinnati,
Ohio, May 1970.
28. ilercer, B. W., ejt _al_. "Ammonia Removal from Secondary Effluents by
Selective Ion Exchange", Battelle-Northwest, October 5-10, 1969.
106
-------
29. Harvey Rosen - Project Manager, Pollution Control System. W. R.
Grace & Co., Davison Chemical Division, Baltimore, Ilarvland,
January 21, 1971. "
30. Eliassen, R. and Tchobanoglous, G., "Removal of Nitrogen and
Phosphorous from Wastewater", Environmental Science and Technoloev
3., No. 6, June 1969.
31. Frauson, F. and O'Farrell, T., "Ammonia Stripping at Washington,
D. C.", U.S. Dept. of the Interior, Federal Water Pollution Control
Administration, Univ. of Pittsburgh, Nutrient Removal Seminar,
February 17-18, 1970.
32. itcMichael, F. W. Samples and F. Vigani, Report on the Removal of
Ammonia from Industrial Wastewater Streams by Air, Appendix A,
llellon Institute, Pittsburgh, Pa., February 1969.
33. Eliassen R. and Tchobanglous, G., "Removal of Nitrogen and Phosphorous
Compounds from Wastevrater", Environmental Science and Technology,
JJ, No. 6, June 1969, p. 536-541.
34. Nusbau, I., J. Sleigh, Jr., and S. Kremen, "Study and Experimenta-
tions in Wastex^ater Reclamation by Reverse Osmosis", Feder Water
Quality Administration, Uept. of the Interior, May 1970.
35. Young, G. R., H. R. lungay, L. M. Brown, and W. A. Parsons, J. Water
Pollution Control Federation, 395-398 (1946).
36. Gunderloy, Frank C., Cliff Y. Fujikawa, V. II. Dayan, and S. Gird,
"Dilute Solution Reactions of the Nitrate Ion as Applied to Waste
Water Reclamation", U.S. Dept. of the Interior, FWPOA, Cincinnati,
Ohio, October 1968.
f
37. Chao, Tyng-Tsair and Wybe Kroontje, "Inorganic Nitrogen Transforma-
tions Through the Oxidation and Reduction of Iron", Proceedings
Soil Science Society of America, 30. 193-5 (1966).
38. Rudolfs, Willem, Industrial Wastes, Reinhold Publishing Corporation,
New York, N.Y. (1953).
39. Frankland, P. F., and Silvester, H. J., J. Soc. Chem. Ind., 2^t No. 6,
231-7 (1907).
40. Fowler, G. J. and Holton, A. L., J. Soc. Chem, Ind., .30, 180-8, (1911),
41. Key, A., "Gas Works Effluents and Ammonia," London, Institution of
Gas Engineers (1938).
107
-------
42. Brown, Ralph L., U. S. Patent 1, 437, 394 (1922), assigned to the
Koppers Co., Inc.
43. Mohlman, F. W. , Am. J. Pub. Health. 19_, 145-56 (1929).
44. Mohlman, F. W., Sewage Works J.. jL9_, 473-7 (1947).
45. Mathews, W. W., Sewage and Industrial Wastes, 24, No. 2,164-30
(1952).
46. Iluller, J. M. and Coventry, F. L., "Disposal of Coke Plant Wastes
in Sanitary Sewer System," Presented to the Western States Blast
Furnace and Coke Plant Association, Chicago, Illinois, January 19,
1968.
47. Morgan, H. H., Knudson, C. II. and Swaney, W. A., "Destruction of
Phenols in Ammonia-Still Waste," United States Steel Corporation,
Pittsburgh, Pennsylvania (1954).
48. Kostenbader, P. D. and Flecksteiner, J. W., Journal Water Pollution
Control Federation, _41, 199-207 (1969).
49. Home, W. R. and llurse, J. E. Proceedings of the Eighteenth Industrial
Waste Conference (1963), 169-173, Purdue University.
50. Ludberg, James E. and Nicks, G. Donald, Water and Sewage Works,
IW/10-13, November 1969-
51. Cousins, W. G. and Uindler, A. B., "Tertiary Treatment of Weak
Ammonia Liquor from Coke I3y-Products Plant," presented at the Water
Pollution Control Federation Meeting, Boston, Mass. (1970).
52. Ashmore, A. G., Catchpole, J. R., and Cooper, R. L., Water Research,
!_._, 605-624 (1967).
53. Delxjiche, C. C. , Inorganic Nitrogen Metabolism, Johns Hopkins Press,
Baltimore, Md. (1956).
54. Fry, B. A., The Nitrogen Metabolism of Micro Organics, Methuen and
Co., London (1955).
55. Alexander, !Iartin, Introduction to Soil Microbiology, John Wiley
and Sons, New York (1961).
56. Ludzack, F. J. and Ettinger, M. B., "Controlling Operation to
Minimize Activated Sludge Effluent Nitrogen", Paper presented to
Water Pollution Control Federation, Milwaukee, Wisconsin, October
(1961).
108
-------
57. Balakrishnan, S. and Eckenfelder, W. W., "Nitrogen Relationships in
Biological Treatment Processes - I. Nitrification in the Activated
Sludge Process", Water Research, _3, 73-81 (1969).
58. Balakrishnan, S. and Eckenfelder, W. W., "Nitrigen Relationships in
Biological Treatment Processes - III. Denitrification in the Modified
Activated Sludge Process", Water Research. 3^, 177-188 (1969).
V
59. Barth, E. F., "Chemical-Biological Control of Nitrogen and Phosphorus
in Wastewater Effluent", J. Water Pollution Control Federation, 40,
2040 (1968). ———
60. Downing, A. L., "Nitrification in the Activated Sludge Process",
J. Institute of Sewage Purification, 2_, 130-158 (1964).
61. Downing, A. L. and A. P. Hopwood, "Some Observations on the Kinetics
of Nitrifying Activated Sludge Plants", Schweizerisch Zeitschrift
fur Hydrologie. 26, 1145-54 (1964).
62. Finsen, P. 0. and D. Sampson, "Denitrification of Sewage Effluents",
The Water and Waste Treatment Journal (England), May/June (1959).
63. Denne, A., and R. Gross, "Industrial Experience with a Plant for
the Biological Treatment of Phenol-Containing Coke Oven Effluents",
Stahl and Eisen, 88, 280, (March, 1968).
64. Fisher, C. W., R. D. Hepner, and G. R. Tallon, "Coke Plant Effluent
Treatment Investigations", Presented at Easter States Blast Furnace
and Coke Oven Association Meeting, Pittsburgh, Pennsylvania, (Feb.*
1970).
65. Gunderloy, Frank C., Jr., Cliff Y. Fujikawa, V. H. Dayan and S.
Gird, Dilute Solution Reactions of the Nitrate Ion as Appliedto
Water Reclamation, U. S. Department of the Interior, Federal Water
Pollution Control Administration, Cincinnati, Ohio. October, 1968.
109
-------
SECTION XIII
PUBLICATIONS
The work performed during the pilot study has been previously described
in the following publication.
Barker, John E. and Thompson, Pvonald J.,
"BIOLOGICAL OXIDATION OF COKE PLANT WASTE"
Presented at Chicago Regional Technical
Meeting of A.I.S.I., October 14, 1971
111
-------
SECTION XIV
GLOSSARY
Aerobe - organisms which require molecular oxygen.
Anaerobe - organisms which live only in the absence of molecular oxygen
Autotroph - organisms that rely entirely on inorganic compounds for
nutritional requirements.
BOD-5 - 5-day, 20 °C biochemical oxygen demand.
C - substrate concentration in reactor.
CCOD - COD concentration (mg/1) .
CD - dilution water conductivity.
Ce - estimated plant cost.
Cg - effluent conductivity or substrate concentration.
Cj - influent substrate concentration.
0^ - liquor conductivity.
Cn - new plant cost.
- nitrate concentration (mg/1).
- nitrate concentration (mg/1) .
cnwmin. - cubic centimeters per minute.
COD - chemical oxygen demand.
Chemosynthetic - organisms which depend on oxidation-reduction reactions
of inorganic substrates for energy for growth.
Complete-mix - a system in which the influent is mixed immediately with
the entire contents of the vessel resulting in a mixture
whose properties are uniform and identical with those
of the effluent.
dia. - diameter.
D_nn - Stoichiometric COD dosage (mg/1) .
e~ - electron
election acceptor - that material that is reduced in biological reactions,
In aerobic systems it is oxygen; in the anaerobic
denitrification system it is nitrogen.
epl - equivalents per liter.
facultative - organisms which can live in either the presence or absence
of molecular oxygen.
ft. - foot.
F - free energy
gal. - gallons.
gpd - gallons per day.
gal/day /ft2 - gallons per day per square foot.
113
-------
heterotroph - organisms which utilize organic carbon for energy and growth,
hp - horsepower.
hydrogen acceptor - the oxidizing agent in biological reactions.
hydrogen donor - the oxidized substrate in biological reactions.
kcal - kilocalories.
kg/cal/mole - kilogram-calories per mole.
K - proportionality constant.
Km - modified constant.
lime-distilled - excess ammonia liquor which has been stripped of fixed
ammonia by increasing the pH to about 11.0 with lime
and passing it through a still.
meq/1 - milliequivalents per liter.
mgd - million gallons per day.
mg/1 - milligrams per liter.
ml/min. - milliliters per minute.
OC - organic carbon.
ppb - parts per billion.
ppm - parts per million.
Q - volumetric flow in the system.
Q - quantity of dilution water.
Q - quantity of liquor.
Lt :' •
r - ratio of new to assumed waste volume.
redox - oxidation-reduction potential.
S - viable organism concentration in reactor.
Seechi disk - a target plate mounted on a calibrated rod which is used
to determine the relative turbidity of water.
sludge bulking - the condition where the solid mass floats in the final
clarifier of a biological treatment plant. This
condition is frequently caused by the denitrification
and the formation of nitrogen gas in the sludge solids.
spent pickle liquor - waste acid which is nearly saturated with iron
from acid cleaning or pickling steel.
SWD - side wall depth.
T - residence time in reactor
T - total required COD (mg/1).
Ov/ls
TPM - tons per month.
2
UMHOS/CM - micro-ohms per square centimeter.
V - volume of reactor.
X - scaling factor.
114
-------
SECTION XV
APPENDIXES
A-l Analytical Data for Excess Aramoniacal
Liquor
A-2 Analytical Data for Effluent from the
Carbonaeious Unit
A-3 Analytical Data for Effluent from the
Nitrification Unit
A^4 Analytical Data for Effluent from the
Denitrification Unit
B-l Analytical and Operational Data for the
Carbonaceous Unit
B-2 Analytical and Operational Data for the
Nitrification Unit
B-3 Analytical and Operational Data for the
Denitrification Unit
C Alkalinity Balance for Nitrification
115
-------
APPENDIX A-l: BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS FROM COKE PLANT WASTES
ANALYTICAL DATA FOR EXCESS AMMONIACAL LIQUOR
DATE
2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
3-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3
4
5
6
7
8
9
10
1
B
I*
j§
H
64
53
52
67
65
62
67
62
55
63
65
67
72
73
60
59
68
72
61
68
61
66
65
65
60
62
64
69
69
74
66
66
61
64
64
70
66
57
58
60
61
70
65
63
77
60
60
62
67
69
65
64
72
63
63
69
69
59
68
66
69
66
68
75
73
71
3.
8.6
8.6
8.6
8.5
8.2
8.8
8.8
8.6
8.8
8.9
8.6
8.6
8.7
9.0
9.0
9.0
9.0
8.9
8.9
8.7
8.7
8.7
8.9
8.8
8.8
8.7
8.6
8.6
8.6
8.8
8.8
8.9
8.9
8.9
8.7
8.6
8.7
8.6
8.7
8.8
8.6
8.7
8.5
8.5
8.4
8.4
8.3
8.8
8.7
8.6
8.9
8.8
8.9
8.3
8.9
9.2
9.0
8.8
8.8
8.7
8.9
8.8
8.8
8.8
8.7
8.7
8.8
8.9
tfsf
M at
35 U
M
I »
<
1580
1460
1340
1280
1000
2060
1740
1660
1680
1660
1530
1410
1290
2920
2700
2590
2510
2720
2370
2300
2240
1940
1970
1960
1830
1810
1540
1620
1400
2280
2030
2060
2030
1870
1710
1675
1645
1485
1580
1552
1475
1455
1375
1200
1300
1150
1100
1795
1750
1580
1625
1640
1625
1200
2700
2700
2750
2600
2550
2390
2400
2075
2250
2020
2085
1950
2070
1985
55
1
u u
t-1
i "t
o
689
706
587
773
809
620
641
880
677
567
890
705
702
913
703
1210
760
1533
1550
1167
1360
1300
1140
1980
2220
1708
3208
2460
2410
3610
OXYGEN
DEMAND,
mg/1 02
•^
B
fl
o
3630
4010
j
H >,
if
g ^
M
RQ
2330
2340
a:
SSA
M "
SB-
S~»
o< g
505
410
501
525
528
778
765
645
930
928
ca 55
S"
>4 M
0 W
12
8
30
21
17
13
33
32
37
47
24
21
24
19
15
20
7.3
14
12
20
8.1
13
37
8.6
34
16
44
19
11
33
i
55
§cn
r*
S °M
H S
250
210
190
240
256
250
240
286
175
274
01
Ea *BO
w g
7
50
23
20
4
23
7
NITROGENOUS
CCMPONENTS ,
Wg/1 N
<
|
s
*
1880
1848
1967
1910
1862
1820
1820
1780
1988
2114
1900
1860
1950
1890
1830
1980
1720
1940
1920
1880 .
1860
1760
2250
1715
2080
2010
2000
1920
1890
3000
a w
| g
g B
o £
101
115
88
92
81
104
88
97
81
69
w
a
as
a
a
w
a
yi
.
H ^f
1-
£C bfl
144
g-
i^
cj e
3130
3644
3704
„
B g
S"5
M
|1
a ^
25 u
o e
13800
17000
14200
14100
14100
13800
10700
11100
12500
11600
12700
13300
12700
12700
11700
13800
12400
14000
13800
13200
14700
12400
13300
12400
12700
14210
12200
12400
12500
20400
117
-------
APPENDIX A-I: page 2 of 6
DATE
4-11-70
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
6-1-70
2
3
4
5
6
7
8
9
10
11
12'
13
14
15
16
17
18
i
L
I"
72
75
69
75
74
72
79
75
67
76
94
68
74
78
66
68
74
66
83
77
77
80
76
81
74
79
78
69
70
75
78
90
84
78
80
88
88
71
80
81
78
88
79
88
78
101
84
87
82
85
83
85
85
87
83
77
87
*
8.6
8.4
8.5
8.6
8.5
8.4
8.5
8.3
8.5
8.3
8.6
8.4
8.4
8.6
8.5
8.2
8.2
8.5
8.4
8.4
8.4
8.5
8.5
8.4
8.7
8.5
8.8
8.5
8.5
8.6
8.6
8.7
8.5
8.5
8.6
8.6
8.5
8.6
8.5
8.6
8.2
8.5
8.4
8.8
8.7
8.6
8.7
8.6
8.5
8.7
8.6
d.6
8.6
8.7
8.7
8.7
8.6
8.6
8.5
8.5
8.5
8.6
8.6
8.7
8.5
8.6
» o"
E 5
if
1 »
1700
1500
2000
1700
1490
1500
1640
2700
1320
1220
1850
1340
1490
1900
1440
1070
1020
1520
1200
1300
1425
1400
1500
1360
2200
2000
1750
1425
1250
890
1860
1800
1650
1380
1750
1750
1590
1960
1740
1900
1400
1500
1250
: 2350
2040
2040
2000
1740
1500
2200
2000
1900
1900
2200
2125
1880
1690
1810
1720
1530
1480
1550
1400
1670
1240
1450
„
9
i ;
a »
It
-
2880
3947
2327
3440
2842
2470
1990
1918
1550
966
1619
1720
1580
1500
1515
2380
822
791
1060
1209
928
1370
1200
2980
1020
713
1414
1400
675
OXYGEN
DEMAND,
ng/1 02
3
i
3400
4140
3620
3
|l
U tf"l
M
0)
1710
2370
M to
i
9S (-1
If
730
1130
846
556
665
850
634
760
700
906
in "
Bf
13
35
18
17
26
17
21
24
34
23
30
31
33
35
34
11
37
37
35
35
24
34
42
41
24
27
40
20
27
1
11
If
240
394
548
400
366
230
98
356
410
360
8"
it
2
2
0
2
3
2
4
6
4
0
0
NITROGENOUS
COMPONENTS ,
mg/1 N
g
i
1760
3810
3230
3330
4240
4100
3500
3740
3190
3210
3490
3330
3370
3640
3610
3250
3540
3420
3150
3080
3120
3150
3300
3570
3420
3860
3770
3930
3720
y S
§i
253
199
116
196
193
224
230
14
375
i
i
1
g
A
1?
if
70
„
§ -.
H 0
3 **.
g f
44
E e
!«
§ u
8-g
12000
24300
21600
24600
27000
25800
23400
23900
20580
21800
20900
19400
21400
24300
22400
19500
21900
20800
21200
18000
19700
26000
20000
20800
21300
23800
22400
25500
29600
118
-------
APPENDIX A-li page 3 of 6
DATE
6-19-70
20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
8-1-80
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
1
3*
S
1
92
86
84
83
90
87
94
91
88
89
89
89
93
88
96
85
85
89
87
94
93
87
88
84
87
88
88
88
88
88
86
88
85
81
91
98
88
88
90
92
87
89
85
93
90
88
88
91
102
90
95
98
88
86
99
88
108
90
106
91
92
86
96
108
90
83
OB
0.
8.5
8.7
8.6
8.5
8.6
8.7
8.6
8.6
8.7
8.5
8.3
8.4
8.4
8.3
8.5
8.4
8.5
8.3
8.2
8.2
8.4
8.5
8.4
8.4
8.4
8.4
8.4
8.3
8.4
8.4
8.3
8.3
8.3
8.4
8.6
8,3
8.6
8.5
8.4
8.4
8.3
8.4
8.4
8.5
8.4
8.6
8.5
8.6
8.4
8.6
8.5
8.5
8.4
8.5
8.5
8.5
8.6
8.6
8.7
8.6
8.6
8.7
8.6
8.6
8.7
8.6
8.5
8.9
S cf
3 u
2 "M
sj
1300
1790
1400
1400
1500
1680
1800
1680
1950
1680
1300
1300
1330
1180
1380
1250
1425
1380
1200
11OO
17OO
1440
1200
1500
1280
1450
1490
1200
1150
1350
1100
1200
1150
1135
1450
960
1550
1515
1640
1550
1220
1600
1400
1510
1350
1600
1400
1750
1290
1420
1650
137O
1130
1720
1400
1550
1650
1480
1580
1150
1580
2150
1600
1390
1610
1560
1925
1880
i
u
a °
BE -i
< --
U &G
272
578
586
272
521
602
834
950
1620
880
OXYGEN
ng/1 02
|
£
g
1770
3380
3650
3340
3390
3440
3190
3440
3370
2990
3160
2920
2880
2910
2700
2960
3140
1310
2920
2580
2729
2790
2740
2970
3079
2910
2860
4010
2360
3
£ «
9 i
w
CO
1830
«t
sf
55 1-1
idt
650
650
580
485
540
420
500
550
706
SB
H°
Sff
19
24
31
28
17
30
25
29
19
34
28
31
22
24
24
27
24
27
27
21
23
25
21
33
26
26
17
19
28
ts
Is
>* (A
O r* •
15f
290
370
350
304
314
300
324
290
426
sV
E-,
5 bo
w S
2
4
2
NITROGENOUS
COMPONENTS ,
mg/1 N
2
§
i
3820
4100
4470
3710
3650
3710
3720
3440
3500
3560
3790
3670
3630
3280
3280
3260
3400
3200
2720
2770
2650
2730
2700
3230
2580
2690
2530
3900
1690
H 0
1 i
o z
179
179
182
154
258
104
106
120
143
1
K
Z
H
es
H
H
„
Ed
1?
« "-<
P "5
CU Q
61
50
g-
M O
O *~>
&~&
o S
SJ5
*•« O
B £
§1
29000
29600
32100
24800
18000
25600
26500
25200
23900
26000
•
28700
28100
27300
24000
23100
26300
23500
23800
20700
20000
18900
20000
19800
22300
17800
18000
18400
27500
10000
119
-------
APPENDIX A-l! page 4 of 6
DATE
8-27-70
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
10-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
16
19
20
21
22
23
24
25
26
27
28'
29
30
31
11-1-70
2
3
If
s
78
85
83
84
88
79
83
84
87
85
89
86
87
90
85
84
84
84
91
87
81
87
85
84
87
84
90
81
84
80
75
72
70
79
75
85
81
79
82
94
83
87
64
70
71
72
70
68
69
67
67
65
65
65
67
73
76
70
72
76
80
76
64
66
65
67
64
62
SB
b
8.2
8.8
8.7
8.6
8,6
8.5
8.6
8.6
8.6
8.6
8.9
8.6
8.5
8.5
8.5
8.6
8.7
8.6
8.5
8.6
8.5
8.6
8.6
8.6
8.6
8.5
8.6
1
8.8
8.5
8.4
8.6
8.7
8.7
8.5
8.6
8.7
8.7
8.6
8.6
8.6
8.4
8.5
8.5
8.7
8.7
8.7
8.7
8.7
8.6
8.6
8.6
8.7
8.8
8.9
8.8
8.7
8.7
8.7
8.7
8.6
8.6
8.7
8.6
8.5
8.6
8.6
8.6
8.8
if
9 C
1540
2100
1850
1270
1950
1250
2045
1230
2080
2100
1720
1700
1950
1920
2150
2160
2580
2640
1900
2700
1970
2340
2300
2250
2300
2020
2400
2340
2350
2230
2280
2280
2260
2250
1920
3050
3025
2650
2760
2600
2640
2450
2120
2500
2480
2450
2260
2270
2275
2000
2000
2010
2300
2500
2600
2315
1975
2130
2140
1850
1800
1800
1660
1660
1850
1820
1660
975
i
8 °
5 ^
i &
OXYGEN
DEMAND,
ng/1 02
g
3B
1
2010
5680
7700
7390
7910
9664
9530
8500
9040
8610
9390
8200
9490
9680
9550
10900
10600
10100
9790
8910
10200
9230
6960
8450
9142
6170
5320
4773
||
SS i
B
6170
5790
2460
.8
P
9S i"^
If
1240
1700
1980
1740
1900
2150
2380
652
8.0
1900
915
*
!8
M *"^
Bf
24
14.1
17
12
8.7
13
15
15
12
20
24
15
26
13
20
21
25
23
14
21
11
8
25
12
28
20
26
1
O **4
iff
440
530
768
1540
628
1100
660
480
540
ft
5 w
W f^
8 ff
2
1
1
1
2
2
4
3
NITROGENOUS
COMPONENTS ,
ng/1 »
a
O
1
1690
3230
3040
2930
3120
3920
4200
4410
4200
4000
4160
3370
3320
3370
3780
4170
4120
4000
3950
3930
3750
3800
4100
4370
4130
3670
3780
3440
O w
•S ffi
1 z
137
146
230
196
165
188
260
230
204
1
H
Z
R
p6
S
,
Ik
o ^^
E ff
49
0.75
34
A
u
S3
O ivl
3 **
iff
_
-
>* ••
Ek
t
S o
§1
12100
22800
22000
20700
21800
26900
28600
30100
28700
28600
28200
23000
20800
23200
23800
26800
28800
27100
28100
28800
27100
27800
28600
29900
29600
26500
27200
25100
120
-------
APPENDIX A-l: page 5 of 6
DATE
11-4-70
5
6
7
8
9
10
11
12
u
1
S--
*
62
59
66
67
77
73
66
67
68
EX
8.8
8.8
8.7
8.6
• Cl
£ 8
i *
s f
1880
2000
2000
1850
8.5 1800
8.5
8.5
8.4
8.5
13 67 8.7
1650
1680
1470
1800
2100
14 60 8.7 i 1570
15 j 60 8.8 2100
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11
52
68
71
68
72
65
70
60
49
86
67
75
74
74
72
73
80
73
74.
71
65
70
71
68
70
57
58
57
64
67
70
71
70
71
73
74
66
66
54
54
68
70
68
60
58
62
70
57
50
50
44
42
50
63
65
8.9
S.8
8.7
8.7
8.6
8.6
8.6
8.6
8.5
8.7
8.5
8.4
8.3
8.1
8.5
8.5
8.5
8.6
8.4
8.4
8.4
8.5
8.5
8.8
8,9
8.8
8.7
8.6
8.6
8.8
8.9
8.3
8.5
8.5
8.6
8.6
8.4
8.6
8.5
8.6
8.5
8.6
8.6
8.7
8.7
8.6
8.7
8.7
8.7
8.6
8.7
8.6
8.5
8.8
8.8
8.7
Z
1
a °
is
t3 00
o
2060
2130
2180
2125
1900
1900
1700
1725
1650
2100
1490
1300
1250
1060
18^0
1750
1725
1650
1320
1575
1520
1320
1325
2650
2550
2300
2280
2100
2130
2550
2400
1900
2180
1600
1950
1800
1600
1900
1930
1650
1560
2450
2180
2560
2425
2170
1920
2270
2020
1950
1980
2050
1800
2500
2425
2220
„ .
OXYGEN
DEMAND,
mg/1 02
a
V
4920
15600
5465
5210
5930
6160
4620
5450
5471
5870
5570
5915
6143
6040
13800
6930
7220
5900
5960
5520
5650
6560
6400
6700
6450
6580
7210
6170
5920
5390
3
J!
a
4160
4030
«l
1!
-f
1070
1080
1110
1120
1480
1180
1100
1290
1310
1010
|-
Bf
26
52
26
17
12
30
23
18
14
30
11
20
21
13
21
35
30
31
34
24
20
22
25
23
20
14
18
12
27
28
1
i!
?»
640
540
560
11
690
692
652
640
648
668
612
1:
£1?
2
3
<1
0.4
1
4
1
4
1
2
NITROGENOUS
COMPONENTS ,
mg/1 N
a
*
3890
4400
3930
4140
3700
3420
3822
3470
3530
4120
3540
3900
3750
3720
3960
4720
3720
4120
4420
4260
4200
2560
2510
2410
2030
1960
2060
1974
2000
2130
li
ii
204
90
140
168
255
176
252
700
2300
2100
13
*
E
g
M
-
If
It
60
52
§3
of
N* C
3-1
> a
II
O -H
u e
27200
31700
28600
30800
26600
24900
26900
24800
27300
28700
27100
28650
27200
28200
27500
33100
28200
28300
31400
32200
31700
30600
28200
28900
30300
28700
30100
31100
32900
29600
121
-------
APPENDIX A-l: page 6 of 6
DATE
1-12-71
13
.14
15
16
17
18
lEHPERATURE
•F
80
82
78
75
62
65
66
X
&
8.7
8.6
8.6
8.6
8.7
8.7
8.7
* C"1
£ 8
H «
S °
3 <
I *
2700
2700
2450
2050
2450
2460
2210
'g
S °
§ <
S f
OXYGEN
DEMAND,
mg/1 02
CHEMICAL
5790
5763
5940
IOCHEMICAI
5- day
m
PHENOLICS ,
mg/1 C6H50H
1200
U ^
s°
11
21
21
32
THIOCYANATE
mg/1 SCN
648
SDIFIDE,
mg/1 S
2
NITROGENOUS
COMPONENTS ,
mg/1 N
|
3950
3976
4450
ORGANIC
NITROGEN
84
i
NITRATE
NITRITE
PHOSPHATE,
mg/1 P04
•
CHLORIDE,
mg/1 Cl
>4 E
CONDUCTIVIT
micromhos /c
28800
29600
29700
122
-------
APPENDIX A-2: BIOLOGICAL REMOVAL OF CARBON AMD NITROGEN COMPOUNDS FROM COKE PLANT WASTES
ANALYTICAL DATA FOR EFFLUENT FROM THE CARBONACEOUS UNIT
DATE
2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
3-1-70
2
3
4
5
6
7
8
9
10
U
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3
4
5
6
7
8
9
10
i
i
8.3
8.3
8.5
8.3
8.3
8.4
8.4
8.4
8.3
8.3
6.5
8.4
8.2
8.1
8.3
8.4
6.5
8.4
8.1
8.2
8.0
8.2
8.1
7.8
8.3
8.2
8.3
8.3
8.3
8.3
8.4
8.1
8.0
7.7
8.3
7.5
6.8
7.5
6.4
6.5
6.9
6.7
6.4
6.3
6.4
6.5
6.4
8.0
8.0
6.9
6.9
6.9
6.9
6.6
7.5
7.5
7.0
7.2
6.7
7.2
6.8
7.0
8,4
8.5
8.3
8.2
8.5
8.5
e
-------
APPENDIX A-2: page 2 of 6
DATE
4-11-70
12-
13-
14
15
16
17
18
19
' 20
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
6-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
|
1*
§
x
8.5
8.5
8.2
8.3
8.3
8.1
8.2
8.0
8.1
8.0
8.1
8.1
8.2
8.2
8.2
8.0
8.0
8.0
7.7
7.8
7.0
7.8
7.9
7.8
8.2
8.2
8.5
8.3
8.2
8.3
8.2
8.3
8.2
8.3
8.2
8.2
8.2
8.2
8.3
8.2
8.2
8.2
8.0
8.3
8.3
8.4
8.3
8.3
8.2
8.3
8.0
8.4
8.4
8.2
8.2
8.3
8.3
8.3
8.3
8.3
8.3
8.5
8.3
8.4
8.1
8.3
K cf
w A
25 U
4 f
500
425
320
375
350
380
360
310
375
335
400
390
420
350
455
400
270
270
240
240
125
275
325
335
600
685
60O
600
450
590
525
550
550
600
600
500
625
725
590
650
600
525
440
700
625
750
675
650
625
790
525
990
920
860
950
975
1360
1020
1070
1010
990
980
450
940
620
700
g
u
0 0
[2 !— 1
0 ^
74
22
44
83
104
66
71
92
66
52
61
150
45
60
64
102
247
62
52
1209
33
148
90
287
92
59
166
613
39
OXYGEN
DEMAND,
mg/1 02
i
o
1700
3
ii
H *°
«
i
wt
s «^.
53 tip
0.2
0.1
0.2
1.0
0.1
0.2
0.2
5.0
0.57
0.60
ss
H
Bff
1.5
0.9
1.5
20
6.2
4.9
3.7
2.8
2.7
3.3
3.9
5.8
4.3
11
4.6
4.7
5.1
10
5.4
35
5.4
5.1
10
6.2
6.0
6.2
5.5
6.2
9.1
i
35
b* tn
g-*^
%
64
79
113
22
164
86
198
180
620
340
I:
VI 6
0.2
NITROGENOUS
COMPONENTS ,
ng/1 N
g
|
399
252
599
788
1120
1220
1360
1150
1190
1170
1400
1700
1510
1640
1640
1690
2020
1970
1652
3080
1760
1720
2100
2440
2560
2860
3040
2940
2860
ll
g g
43
45
59
59
76
87
200
161
196
200
1
H
X
1.0
0.8
1.1
3.7
6.3
6.3
2.9
6.6
5.4
7.3
6.9
5.1
5.9
4.6
2.3
1.5
1.5
0.7
1.0
0.5
0.5
0.1
0.1
0.3
0.2
0.2
0.5
0.3
1
g
B"*
1?
M 00
^ 3
„
3^
if
>« 6
P 5
B^
H|
5S W
O S
4000
3510
5680
7480
9820
9860
10780
9560
9390
9730
11000
12500
,
12600
14000
12200
13300
15000
14700
14100
18000
13200
14900
14600
16600
17400
19400
20300
21700
23500
124
-------
APPENDIX A-2: page 3 of 6
DATS
6-19-70
20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
. 15
16
17
18
19
20
21
22
23
24
-1 25
26
27
28
29
30
31
8-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
1
•f
1
X
a
8.1
8.3
8.3
8.1
8.2
8.2
8.2
8.1
8.2
8.1
8.0
8.1
8.0
8.0
8.0
8.0
8.0
7.8
8.0
7.9
8.0
8.0
8.0
8.1
8.0
8.0
8.0
8.0
7.8
8.0
8.0
7.9
8.0
8.0
8.3
8.0
8.1
8.1
7.9
7.7
7.9
7.9
8.0
8.0
7.9
8.2
8.0
8.2
8.0
8.2
8.1
8.1
8.0
8.2
8.2
8.2
8.2
8.1
8.1
8.2
8.2
8.6
8.2
8.1
8.1
8.2
8.2
8.0
BiT
M «
55 O
!* f
360
525
475
375
525
365
640
475
475
415
380
325
325
325
350
425
430
280
500
520
375
350
355
400
325
380
340
400
185
350
350
310
400
380
550
420
480
540
430
235
400
415
525
550
415
640
390
660
435
550
475
510
460
450,
620
565
515
540
455
530
475
720
470
525
445
535
550
485
.
1
O O
W
ii
Otf E*
24
51
43
22
18
33
53
41
72
OXYGEN
DEMAND,
mg/1 02
i
u
1030
875
955
1000
667
719
645
716
727
725
803
532
512
546
793
867
1140
816
788
696
725
665
695
707
777
774
1190
895
903
3
g "O
M
-g
CO u*1
U S
§*
11
0.34
0.2
0.2
0.2
0.2
0.3
0.2
0.17
.30
bl Z
S"
si
6
4.2
4.4
5
4
6.7
9.1
11
5.6
4.7
3.5
3.7
3.1
3.5
4.3
5.0
5.0
6.3
5.5
5.0
4.3
4.7
6.1
8.5
4.9
4.5
4.6
6.0
5.7
IS
ft* CO
t-t *""«
Ef
240
154
164
174
174
190
250
220
274
8«
B-
If
0.6
NITROGENOUS
COMPONENTS ,
mg/1 N
I
1
1810
1820
2180
2320
1740
1790
1840
1880
1920
1760
1580
1670
1270
1620
1760
2240
1920
2160
2220
1880
1820
1740
1780
1850
1940
1700
1670
1710
2240
55
as
5S
O H
S £
98
102
42
88
143
119
80
92
84
1
H
^ H
SE
-
0.2
0.2
0.4
0.2
0.1
0.3
0.4
0.3
0.4
0.3
0.2
0.4
0.7
0.3
0.3
0.3
0.4
0.4
0.3
0.6
1.1
1.0
0.5
0.8
0.5
1.4
0.5
0.3
S
S
a
K
EC
\€
EO »-i
11
g-
g-
o
1^
M O
i!
§0
•rt
U S
15600
15100
18100
17800
15100
15600
15800
15400
15300
14400
13800
14900
11200
14100
14400
19700
16400
18000
18800
16500
15100
14300
14400
14700
15900
13800
14400
14700
18400
125
-------
APPENDIX A-2: page 4 of 6
DATE
8-27-70
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
; 23
24
25
26
27
28
29
30
10-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
11-1-70
2
3
i*
i
X
7.7
8.0
8.2
8.0
8.1
8.1
8.1
8.0
7.9
E C
a ^
1 ~*
500
575
650
335
415
500
575
575
490
8.0 550
7.9
; 7-S
7.8
7.8
7.8
7.8
8.0
7.9
7.8
8.0
7.8
7.9
7.7
7.9
7.9
7.8
7.9
8.0
7.9
7,9
7.9
7.8
8.2
7.8
7.9
18.1
8.0
8.0
7.9
8.1
7.8
7.9
7.8
8.0
8.1
8.0
8.1
8.1
8.0
8.0
8.1
8.0
8.1
8.2
8.1
8.1
7.9
8.0
8.0
8.0
8.0
8.0
8.0
8.0
8.0
8.2
8.2
8.3
475
300
410
340
550
475
660
560
465
675
590
670
540
625
575
475
650
640
550
575
625
575
825
475
645
980
955
900
725
725
560
550
380
475
450
420
420
380
350
325
375
400
295
340
375
350
330
365
375
360
345
400
425
480
525
540
370
525
z
u u
2 *"*
i ^
,
OXYGEN
DEMAND,
ing /I 02
i
i
900
693
785
2960
1250
1319
1850
2060
2440
2390
2380
2240
2020
1993
2740
2330
1550
766
629
583
602
567
732
807
895
592
1*
g*>
ta
i
.8
as
jS £0
.22
0.2
0.90
i
1.1
1.2
11
16
0.2
0.2
0.2
*!
1^
4.6
2.7
3.3
4.1
4.3
5.0
4.6
4.6
2.4
5.4
5.8
8.4
5.9
5.9
5.6
5.0
3.4
1.7
2.0
1.2
1.6
1.8
2.9
2.8
8.5
3.0
IB
ll
144
270
,
'
394
1220
394
628
150
220
190
1:
B u
w s
NITROGENOUS
COMPONENTS ,
mg/l N
|
|
1870
1040
1530
1920
1730
1890
2480
2600
2860
2630
2520
2480
2160
238
2340
2020
1350
686
520
504
658
700
931
1140
1510
1080
•1
1 i
98
115
176
153
77
80
99
74
62
1
H
Z
0.6
0.8
0.4
0.1
0.3
0.2
0.1
0.3
0.6
0.1
<0.1
0.3
0.2
0.3
•
0.5
0.3
0.4
0.2
0.3
0.3
0.4
0.5
0.3
0.2
0.4
0.1
B
i
•'<
Ik
§ i
a"-
M CJ
s c
fi3
u IP
IDUCTIWITY
iromhos/cm
ft w
81
15200
9630
14000
15800
14600
16300
20600
21400
23200
22400
21500
20000
17600
17000
19800
16800
12500
6240
5100
5040
6010
6600
8700
11500
12900
9740
126
-------
APPENDIX A-2: page 5 of 6
BATE
^\
11-4-70
5
6
7
.. 8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
.,12-1-70
2
3
4
5
6
7
8
9
10
II
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
1-1-70
2
3
4
5
6
7
• 8
9
10
11
nm^mmmmmiiiifm
!r
mttffftft^fmfrmm
X
o.
8.3
8.4
8.2
8.2
8.1
8.0
8.0
8.0
8.1
8.2
8.3
8.3
8.4
8.2
8.2
8.2
8.2
8.2
8.2
8.2
8.2
8.2
8.2
8.0
8.0
8.0
8.1
8.1
8.1
8.2
8.0
8.1
8.1
8.0
8.0
8.2
8.4
8.3
8.2
8.1
8.1
8.3
8.3
8.3
8.1
8.2
8.1
8.1
8.0
8.0
8.0
8.1
8.1
8.1
8.2
8.2
8.2
8.5
8.3
8.2
8.3
8.3
8.2
8.2
8.0
8.2
8.2
8.1
**M>*qBBM^
ALKALINITY,
mg/1 CaCO,
560
570
725
690
650
575
595
580
625
625
660
750
825
1625
575
520
425
400
400
400
380
390
380
325
300
, 280
320
350
340
350
320
400
350
280
300
490
600
650
570
525
510
600
525
5OO
500
520
440
510
450
410
460
460
580
625
650
660
625
510
645
600
580
550
450
325
35O
575
415
424
§
s °
3 <
1 »
«»MM«MM^.wn_
OXYGEN
DEMAND,
rag /I 02
CHEMICAL
672
1680
928
1030
1080
1280,
697
658
582
419
344
445
417
516
538
517
782
840
729
688
698
692
660
757
654
594
646
727
767
764
CHEMICAL
5-day
o
M
ra
-g
i3£
H iO
Si °
!~i
0.6
4.3
0.4
0.1
0.1
0.2
0.1
0.3
0.2
6.3
-
tans
8°
S~
Ss^J
o 3
3.1
6.4
5.0
5.5
12
12
3:8
2.4
2.7
2.6
2.2
2.9
4.9
4.0
3.3
4.8
7.4
5.0
6.4
6.3
6.1
e.i
4.7
5.6
5.01
4.3
4.4
5.0
4.8
5.4
H.l^^^»»
si z
fis
O P-4
gff
290
306
140
180
250
280
280
284
284
294
S»
V,.,
^ bfl
M S
-------
APPENDIX A-2: page 6 of 6
DATE
1-12-70
13
14
15
16
17
18
19
20
i
I*
Mo
i
'X
&
8.2
8.1
8.2
8.1
8.2
8.3
8.2
•
B 8"
SB! O
h>) •-<
i *
450
525
615
540
625
575
525
i
1
t) O
Z tH
1 *
OXYGEN
DEMAND,
ng/1 02
2
H
1
754
659
689
674
d
I i«
g] "O
r
ca
'
'
A
B *
o
if
0.2
SS
RP
Iff
5.7
5.4
4.7
3.8
1
|s
u
Iff
284
B w
W
ll
NITROGENOUS
COMPONENTS ,
mg/1 N
g
SB
•|
1690
1680
/
1670
1250
g 1
5 s
II
70
s
5
g
0.6
0.8
0.8
1.2
S
•M
g
'
B .»
i ^
W KM
1 f
A
i G
?3 •-!
M ***
A
&•» B
64
M O
& B
z u
O •H
u e
14200
14000
13500
11700
128
-------
APPENDIX A-3: BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS FROM COKE PLANT WASTES
ANALYTICAL DATA FOR EFFLUENT FROM THE NITRIFICATION UNIT
DATE
2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
3-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3
4
5
6
7
g
9
10
_ _ i
1
I'
1
'£
6.5
6.6
6.7
7.5
6.4
6.4
6.4
6.9
6.7
7.0
6.9
7.0
6.6
7.2
7.2
6.5
8.5
6.8
6.3
6.4
6.4
6.6
6.5
6.3
6.3
6.3
6.2
6.2
6.4
6.4
6.3
6.4
6.2
6.7
6,7
6.7
6.2
6.4
6.0
6.4
6.5
6.5
6.3
6.1
6.0
6.3
6.3
6.5
6.5
7.0
6.5
6.7
6.5
6.3
6.4
6.3
6.2
6.2
6.0
6.4
6.5
6.5
7.1
8.3
6.6
6.3
6.3
6.4
• M
4 O
ALKALINI:
ng/1 Cai
136
85
86
95
174
47
48
91
79
71
95
95
869
118
162
126
443
105
80
70
100
100
90
90
90
110
75
45
45
50
45
65
60
75
50
50
60
40
55
40
100
50
45
35
60
55
45
120
55
75
105
70
75
50
45
125
55
55
70
68
90
60
75
225
40
30
30
55
§
i
s °
5 *H
1 f
54
35
37
39
36
36
39
36
27
27
21
23
21
17
16
19
18
10
16
13
16
18
13
23
16
23
39
27
16
15
OXYGEN
DEMAND,
rag /I 02
1 CHEMICAL
HXM-^B^—^-
d
if
r
-8
£A l*n
3 ae
i "
If
- —
CYANIDE,
ingA CN
s
is
K
Bff
10
9
10
i ^ ii "
g"M
E-
If
•
NITROGENOUS
COMPONENTS ,
ng/l N
|
213
186
160
200
237
225
161
160
200
164
141
178
167
132
81
97
136
151
178
206
147
241
221
197
216
310
302
144
62
29
, ORGANIC
NITROGEN
NITRATE
.
47
33
47
56
52
51
71
70
74
68
70
70
70
80
97
90
93
84
87
87
95
102
96
126
87
96
131
122
96
135
NITRITE
48
34
39
48
48
50
55
59
59
51
63
64
56
67
75
91
94
76
69
64
73
63
75
90
110
107
147
128
95
116
Dd
PHOSPHAT
mg/1 ?04
*
CHLORIDE
ng/1 Cl
486
486
523
P* fi
•4 0)
55
II
Si
2920
2790
2620
2860
3100
2990
2390
2420
2500
2280
2570
2810
2890
2580
2100
2630
2840
2820
2840
3250
2790
3030
3110
3250
3520
4230
3860
2500
2520
129
-------
APPENDIX A- 3: page 2 of 6
DATE
4-11-70
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
6-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
TEMPERATURE
°F
£
6.8
6.4
6.2
6.7
6.5
6.4
6.7
6.5
6.9
5.8
6.7
6.7
6.7
6.9
6.6
8.0
7.9
7.5
6.8
6.8
7.7
6.8
6.8
9.0
8.6
8.3
8.4
8.0
7.6
6.4
6.2
8.2
8.3
7.8
7.5
7.5
7.5
6.6
6.3
6.7
6.4
6.4
6.7
7.2
7.5
7.5
7.8
8.0
8.0
7.9
7.9
8.2
8.0
8.0
8.0
7.0
8.0
8.0
7.3
6.7
6.3
6.6
7.0
6.1
6.7
6.4
ALKALINITY,
mg/1 CaCOj
500
40
35
50
45
50
45
40
60
60
75
65
70
75
65
:380
185
135
70
75
240
80
105
1120
715
500
450
300
120
15
35
300
400
215
160
180
145
40
40
25
20
20
25
135
100
140
220
370
360
175
140
250
245
(240
240
205
180
145
75
20
25
20
75
20
25
25
^
o o
M
§ <
g f
O
55
28
16
48
74
86
74
88
49
27
41
142
30
9
48
109
48
4
4
24
26
29
22
27
39
44
73
73
39
OXYGEN
DEMAND,
mg/1 02
CHEMICAL
"
£J *O
H
ea
M "")
0 EC
M %D
At
gg
M
Si
* .'»'
Bl
e-
M B
NITROGENOUS
COMPONENTS ,
mg/1 N
AMMONIA
136
223
193
416
728
994
609'
840
644
553
777
1360
567
259
1140
1620
875
364
182
749'
1430
1740
567
343
154
112
106
8
36
ORGANIe
NITROGEN
NITRATE
160
83
103
192
224
130
115
,296
400
441
366
61
34
66
45
,
21
50
63
54
w
131
103
,4.3
0.6
0.5
4.8
10
17
66'
108
NITRITE
i
182
122
230
254
220
i
172
185 '
283. '->
405
369
314 •"•
.
70
34
52
53
47
63
66
106
135
96
7.4
1.2
0.51
3.4
4.8
3.9
! 91
105 .
PHOSPHATE,
mg/1 P04
CHLORIDE,
mg/1 Cl
:'
CONDUCTIVITY
mlcromhos /cm
4230
4040
5400
7750
10300
10300
10780
11300
11300
12800
11400
12200
5940
3530
11000
13000
8400
4310
3370
8150
12900
15600
4640
3310
1800
1940
1910
2060
2540
130
-------
APPENDIX A-3: page 3 of 6
DATE
6-19-70
20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
8-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
1'
H
X
ca.
8.0
6.7
6.8
6.5
6.4
6.8
6.8
6.4
6.4
6.6
7.0
8.1
7.6
9.9
8.3
7.5
6.4
6.5
6.5
6.6
6.9
6.9
6.8
6.8
6.8
6.7
6.7
6.7
6.8
7.7
6.7
6.7
6.6
6.7
7.2
8.0
8.0
7.8
7.7
7.7
8.0
7.9
8.0
7.8
7.4
6.7
6.6
6.4
6.8
6,7
6.6
6.6
6.5
6.5
6.2
6.6
6.6
6.6
6.5
6.6
6.4
6.4
8.8
8.5
8.4
8.4
8.3
8.1
I »
105
40
35
25
25
70
50
40
40
60
75
125
190
400
210
100
25
25
25
35
50
50
40
35
35
30
50
50
40
130
30
30
65
55
80
220
275
245
230
135
2OO
145
160
120
85
35
25
25
25
60
20
20
60
60
50
55
45
20
2.0
15
55
20
345
255
210
205
220
185
1
U
g »
o
24
17
43
6
7
18
21
32
31
25
1
OXYGEN
DEMAND,
tug /I 02
a
°
219
213
277
404)
227
89
318
343
309
373
380
295
381
426
555
140
58
81
94
85
74
82
66
90
171
142
178
OCHEHICAL
5- day
g
il
5 9
*.
3 OB
o 9
Is
8 tf
u
g:
eft C?
!
NITROGENOUS
COMPONENTS ,
mg/1 N
i
1
136
100
134
61
69
27
197
228
262
232
214
239
277
361
339
899
1090
378
123
104
104
137
126
48
73
82
161
207
326
il
8 &
1
g
111
183
142
174
200
223
173
60
161
109
102
124
124
147
142
77
1
32
4.9
43
29
38
35
38
25
41
45
40
4.8
11
1
5
140
154
174
186
199
298
203
63 .
i
142
,
149
135
162
.
158
115
131
88
4.2
3.2
25
47
51
47
47
41
41
43
32
6.9
15
t? e?
GO i-*
Bi tf
Is
£c oo
5 s
k. . ea
>in»cTivm
Lcrotnhos/cn
u e
4020
3890
4470
3840
4690
5680
4480
5180
4820
4730
5550
5610
5620
5830
10200
1020
4040
2170
2080
2030
2260
2240
1430 '
1690
1740
2640
2680
3850
131
-------
APPENDIX A-3: page 4 of 6
DATE
8-27-70
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
10-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
11-1-70
2
3
W
i?
1°
X
o.
7.7
7.8
7.5
6.7
6.7
6.8
6.4
6.6
6.9
6.8
6.5
8.3
6.9
6.6
6.8
6.9
7.1
7.1
7.2
7.4
7.1
7.0
6.9
7.0
6.9
6.8
'7.1
7.0
7.0
7.2
6.7
6.7
7. 4
6.8
6.9
7.0
7.1
7.0
6.6
6.8
6.5
6.6
6.8
6.9
6.5
6.7
6.7
6.7
6.5
6.8
6.8
6.8
6.8
6.7
8.7
10.1
6.5
6.8
6.7
6.8
6.7
6.5
6.7
7.3
7.3
6.8
6.7
9.7
- Cl
S- O
H U
H
si
165
140
100
35
25
80
30
25
50
50
40
210
40
45
50
60
80
85
100
120
115
100
80
90
75
75
100
75
80
90
55
65
120
60
75
75
90
75
45
60
60
65
65
65
35
45
45
45
65
45
50
55
75
135
200
430
45
65
60
75
50
50
50
215
125
65
60
975
g
O
M
Cj) 00
OXYGEN
DEMAND,
mg/I 02
t>
u
218
185
152
351
384
468
535
556
620
612
672
681
668
637
552
620
712
603
500
471
517
512
510
381
719
396
480
524
g
II
M
CQ
M-§
|l
W *"*•"
1 f
|§
Stf
l»
ll
l-l "-.
Bf
p™
co 6
NITROGENOUS
COMPONENTS ,
tng/1 N
5
s
482
148
134
130
284
167
237
330
421
384
398
347
428
213
104
90
322
302
230
126
123
92
.76
22
145
220
2.3
154
„ „
ii
1
g
13
40
31
157
142
11
136
212
181
147
215
203
147
212
303
316'
"
286
263
162
313
348
339
392
70
551
384,
203
279
|
1
21
)
48
48
165
128
12
196
225
209
225
235 [
26?.
220
"
280
272
245
223
213
183
234
253
275
377
210
431
159 .
168
287 ,.
B *
§-^
93 U
1
*
1"
11
EM B
II
H JS
§ U
O -H
u e
4990
2490
2230
4150
5300
5380
6060
8050
7830
7560
7430
7880
6490
5260
5500
7430
6560
5420
5230
5940
6130
6180
5270
8510
5330
5150
6530
132
-------
APPENDIX A-3: page 5 of 6
DATE
11-4-70
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11
i
.TEMPERAl
•P
ac
a.
8.8
8.6
8.2
7.6
6.7
6.8
7.1
6.9
6.9
7.0
6.8
6.8
7.0
7.0
6.7
6.7
6.7
6.9
6.9
7.0
7,5
6.8
6.7
6.5
6.4
6.6
6.9
6.8
6.8
6.9
6.9
6.8
6.7
6.8
6.6
6.6
7.0
7.0
7.5
6.7
6.9
6.9
6.8
8.5
6.7
6.9
6.6
6.7
6.7
6.9
6.8
6.9
6.8
6.9
7.0
7.0
7.2
6.9
6.7
6.7
6.6
6.9
7.1
6.7
7.2
8.1
8.0
7.4
• •'
520
35
76
40
40
50
70
60
60
50
60
55
85
160
55
60
50
65
85
115
50
130
250
205
80
.
O
u o
M
3 *i
1 »
OXYGEN
DEMAND,
mg/1 02
CHEMICAL
280
227
265
332
319
301
275
266
562
245
422
470
409
405
408
438
511
406
404
375
328
375
417
460
477
383
534
479
384
384
4
BIOCHEMIC
5- day
.§
CA in
O X
M vD
tJ U
S5 i— '
3 ob
W E
CYANIDE ,
mg/1 CM
i
Is
§n
w -*.
EC ep
H E
SULFIDE,
mg/1 S
NITROGENOUS
COMPONENTS ,
mg/1 N
AMMONIA
284
382
568
588
381
465
339
185
30
129
137
20
48
73
96
157
24
56
148
.82
312
255
78
66
7.4
97
129
185
211
260
ORGANIC
NITROGEN
NITRATE
84
77
44
54
72
98
79
105
197
81
165
213
224
170
260
161
233
213
167
125
109
158
238
210
282
209
260
224
171
85
NITRITE
0.08
0.01
<0.01
0.05
0.13
0.31
0.03
0.02
<0.01
<0.0
0.01
211
250
250
260
279
225
200
205
130
110
180
196
190
255
175
257
195
85
30
*
&d
|g
cu
M *-*
S-~
0"
CL. f
CHLORIDE,
mg/1 Cl
*
ii
CONDUCTS
micromho!
5150
4720
6490
6690
6340
6270
5440
4270
4440
3700
4150
5170
4910
5140
5720
6100
5230
4400
4950
3380
5340
5850
5600
5350
5490
5600
7460
7370
6360
7080
133
-------
APPENDIX A-3: page 6 of 6
DATE
1-12-70
13
14
15
16
17
18
19
20
TEMPERATURE
•F
s.
6.8
6.9
7.5
7.0
7.0
7.1
6.8
ALKALINITY,
rag/1 CaCOj
45
55
470
65
75
70
55
z
s «
OXYGEN
DEMAND,
mg/l 02
CHEMICAL
303
329
337
362
IOCHEMICAL
5- day
00
FHENOLICS ,
mg/l CfcHsOH
u z
Q U
If
THIOCYANATE,
mg/l SCN
S«
K-
NITROGENOUS
COMPONENTS,
mg/l N
AMMONIA
594
552
454
417
si
NITRATE
81
193
160
160
•
NITRITE
71
116
125
139
•7
\&
§t~4 •
60
B. f
CHLORIDE,
mg/l Cl
f.
CONDUCTIVITY .
mlcromhos/cm
7200
7030
6120
6410
134
-------
APPENDIX A-4: BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS FROM COKE PLANT WASTES
ANALYTICAL DATA FOR EFFLUENT FROM THE DENITRIFICATION UNIT
DATE
-,
2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27 >
28
3-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3 t
4
5l
6
7
8
9 :
10
I
is-
i
^
•
,
__ — -
EC
Cu
6.4
6.4
6.5
7.3
7.1
6.9
7.0
7.0
7.0
7.5
7.5
7.4
6.7
7.4
7.4
7.3
6.5
6.4
; 6.4
: 6.7
6.6
7.2
7.1
6.6
7.4
7.0
7.1
7.3
7.4
7.3
7.6
7.0
7.8
8.0
8.3
8.0
8.0
8.3
7.8
7.3
6.9
6.7
7.2
7.0
6.5
7.3
7.4
7.3
7.9
7.0
7.2
6.9
7.0
6.9
6.7
7.1
6.4
6.5
7.0
7.4
7.4
7.8
7.8
8.1
7.7
7.7
7.7
8.0
*
1
J U
h
159
196
96
29
29
30
37
40
30
31
24
24
28
16
14
24
15
24
45
37
43
28
36
43
84
40
46
28
. 20
16
ii -••
OXYGEN
DEMAND,
mg/1 02
CHEMICAL
418
470
^
\ «
1?
j in
>
M
«
193
*
'
105
,
• —
„•&
PHENOLIC:
mg/1 CbH
^ ^— ^—
U 2S
S°
5^
Bff
«
\l
gf
12
8
8
SULFIDE,
mg/1 S
NITROGENOUS
COMPONENTS ,
mg/1 N
AMMONIA
188
179
155
193
213
220
169
147
186
157
126
151
142
116
56
74
102
131
153
197
134
227
224
176
179
265
322
147
90
71
ORGANIC
NITROGEN
45
29
43
28
24
26
34
26
35
28
NITRATE
48
14
11
0.1
4.7
1.1
11
69
56
24
14
19
1.2
28
16
2-1
1.1
52
1.1
1.4
1.4
1.4
1.7
1.7
0.5
1.0
0.6
52
38
24
NITRITE
44
15
10
0.05
2.8
0.2
7.8
59
51
13
8
16
0.01
22
10
2.7
1.0
48
0.01
0.01
0.16
0.11
0.02
0.02
0.05
0.01
0.01
53
29
35
W
isf
§**^
60
ex E
24
.
CHLORIDE
mg/1 Cl
468
468
498
^ s
t-Z.
CONDUCT I
micromho
2900
2650
2620
2860
2820
2830
2230
2370
2410
2140
2220
2510
2610
2330
1800
2270
2430
2615
2560
2970
2410
3070
3110
2830
3070
3600
4000
3550
2650
2540
135
-------
APPENDIX A-4: page 2 of 6
DATE
4-11-70
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
. 23
24
25
26
27
28
29
30
31
6-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
1
flfi Du
s*
B
.
i
8.7
8.3
8.1
8.5
8.5
8.3
8.0
7.6
8.3
8.0
8.1
8.0
8.0
8.2
7.9
7.2
8.0
8.0
8.0
8.2
7.9
7.6
8.0
8.9
8.8
8.4
8.4
8.2
7.9
7.9
7.9
8.1
8.6
8.2
7.8
7.9
7.8
7.5
7.4 '
7.6
7.4
7.0
6.7
6.8
8.4
7.8
7.7
7.9
7.7
7.7
7.1
6.9
7.3
7.3
7.1
7.1
7.0
7.1
7.3
7.4
7.5
7.8
7.9
8.3
7.8
7.1
8.1
» fO
E 1
H4
d C
1 »
475
320
460
415
385
400
290
220
460
375
420
425
375
500
375
75
385
340
360
450
425
450
475
935
1100
850
790
550
325
285
300
400
775
540
460
480
465
370
335
315
315
180
10.0
150
675
550
550
550
450
450
280
190
260
240
210
220
205
230
260
290
310
380
375
450
340
220
275
1
o o
^H
3 -*•
i $
65
44
30
44
68
290
102
129
110
41
40
159
82
55
44
166
65
15
32
23
53
53
50
67
61
60
76
75
20
OXYGEN
DEMAND,
mg/1 02
j
u
tj
U
1000
1590
520
w ^
S *
a -a
a
141
734
«l
^a u
g ,_,
£* W
af z
5 u
If
§ £§
fn VI
o *-•
fSf
»
£-1 Cfl
fi-
g's
01 6
NITROGENOUS
COMPONENTS ,
mg/1 N
I"H
§
1
112
189
139
391
626
882
980
875
595
52*
616
1170
812
343
966
1550
1210
490
273
371
1190
1610
812
469
196
160
176
82
90
US
^^ 55
§ §
Is
28
28
62
70
43
59
49
78
14
20
1
s
g
35
0.1
82
141
124
66
58
189
339
328
376
22
0.1
0.1
0.1
0.1
0.1
0.1
44
8.1
0.4
0.1
0.1
0.2
0.1
0.2
0.2
0.1
,
51
!
s
K
s
43
0.05
11
169
124
> 85
92
229
293
405
357 '
16
0
0.02
0.01
0.01
0.02
0.01
93
9.1
0.01
0.03
0.03
0.03
0.05
0.06
0.02
0.02
40
jV
35 CM
C/l *-<
8»
,
i
i
16
36
.s-
" W O
§ ~-
it
>-" 8
H u
> a
y K
a u
ll
3440
3570
4700
7230
9000
10300
10180
11100
10810
11800
11200
12500
7920
4210
9560
3100
0500
5240
4000
5070
0700
4000
7130
4710
2480
2270
2340
2190
2700
136
-------
APPENDIX A-4: page 3 of 6
DATE
6-19-70
20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
8-1-70
2
3
4
5
6
7
8
9
10
H
12
13
14
15
16
17
18
19
20
'•• 21
22
23
24
25
26
L
*
H
i
33
CL
8.5
8.8
8.9
8.6
8.7
8.7
b.b
8.5
8.5
8.8
8.')
9.0
!
MI i ' —
9.0
9.3
9.0
8.4
7.9
7.5
8.3
8.3
8.6
8.5
8.6
8.6
8.4
8.8
8.6
8.4
8.5
8.8
8.3
8.2
8.5
8.4
8.2
8.2
8.1
7.9
6.9
6.7
7.3
6.6
7.0
7.0
7.2
7.5
7.5
8.0
7.6
7.9
7.7
7.8
7.8
7.8
7.5
6.9
7.2
7.6
7.8
7.8
6.5
6.9
8.2
8.2
8.1
7.6
7.3
7.6
im
" to
El
g «
3 F?
M B
425
500
575
430
560
525
570
380
400
560
450
620
600
525
875
480
300
280
450
400
565
520
540
540
475
515
450
385
520
745
375
385
475
460
500
515
460
370
270
245
250
250
225
210
235
280
340
415
315
285
305
345
375
360
260
240
155
210
280
295
40
50
435
405
350
325
310
350
i
u u
•4
5 v"4
< "^
8 i
o s
73
32
13
7
10
26
35
292
150
OXYGEN
DEMAND,
ng/1 02
3
a
H
U
313
184
515
367
390
487
504
565
409
469
464
392
466
437
410
504
1400
1140
494
573
262
360
292
596
322
67
933
743
691
^
-» x
S3
g"1
3
266
189
OLICS ,
C6H50H
S5 i— '
1"5
a ff
•"—
ta 55
O U
H
2 _<
!"»
s t
"
CYANATE,
SCN
o <-<
H *-*
T* fj.
H i
S'o,
E i-4
i"«
w 5
—
NITROGENOUS
COMPONENTS ,
mg/1 N
g
XJ
*
190
133
202
94
132
92
164
265
228
216
204
190
281
330
308
759
1170
750
174
146
148
182
171
78
113
124
85
209
258
" —
0 S
si
< ft!
S S
o z
26
27
30
30
34
21
22
16
24
B
H
Z
3
45
158
96
48
129
0.3
0.2
20
3.8
7.2
35
2.0
0.3
16
0.1
0.2
0.4
0.2
0.1
0.3
0.1
0.3
0.1
0.5
40
0.3
0.1
0.2
§
OS
a
rH
z
2.8
47
14
120
52
130
0.02
0.03
24
4.4
7.3
31
3.4
0.01
19
0.01
0.01
0.06
0.01
0.01
0.47
0.02
0.09
0.05
0.01
43
0.01
0.01
0.08
Id"
I2"
CO **
Q "^
a, f
33
39
H U
S 00
U S
»T e
s|
•4 O
~* *S
5 U
' "rf
U E
3800
3930
4320
4480
4540
5320
3760
4330
4360
4140
4400
9300
4670
5180
8910
10800
7540
2600
2390
2360
2570
2580
1760
2030
2150
2200
2980
3500
137
-------
APPENDIX A-4: page 4 of 6
DATE
8-27-70
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
1 '10- 1-70
2
3
4
5
- '&'
7
"'8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
... 28'
" 29
30
31
11-1-70
2
3
3*
H
35
B.
7.3
7.4
7.4
7.3
7.7
9.0
8.0
8.2
8.6
8.5
7.7
8.5
E.8
8.6
8.5
8.5
8.5
8.5
8.5
8.4
8.4
8^3
8.2
8.3
8.4
8.3
8.3
8.4
8.2
8.3
8.5
8.5
8.5
8.7
8.9
9.0
9.2
9.0
8.7
8.6
8.2
8.3
8.4
8.4
8.0
8.5
8.8
8.9
8.9
9.0
9.0
9.1
9.1
9.2
9.2
9.5
9.2
8.8
9.1
9.1
9.1
8.9
8.9
9.0
9.4
9.0
9.0
9.5
- C*l
>< O
s 3
•s °
I "
s3 *
295
290
300
305
390
675
350
500
475
550
925
590
760
665
675
710
800
875
775
740
700
750
580
640
725
675
715
660
575
550
640
625
650
700
750
710
780
830
725
775
650
650
640
700
700
780
830
960
1045
950
930
1000
980
925
835
920
1175
1000
1035
1435
1225
900
775
900
1020
1005
950
1200
§
a °
s<
i f
OXYGEN
DEMAND,
mg/1 02
a
o
629
544
456
468
563
605
684
558
657
596
1350
605
668
691
626
788
931
690
587
683
1750
1130
792
1130
1015
587
926
974 .
H X
w "O
O lA
5
136
362
-g
SS
M VO
^ °
|~
It
gg
§=:
ff U)
u I
IOCYANATE
/I SCN
gf
1:
M e
NITROGENOUS
COMPONENTS ,
mg/1 N
jjjj
1
479
255
112
119
254
167
208
296
386
378
367
367
414
207
137
64
202
258
252
204
148
116
55
120
190
207
1.1
160
GANIC
TROGEN
8 £
25
33
43
172
40
375
60
42
97
1
g
0.2
0.2
0.2
17
0.2
11
15
0.4
2.9
18
17
40
57
67,
99
80
115
.114
i.
22
3
45
78
131
8
1.4
11
33,,
15,,. .
1
w
•z.
0.18
0.03
0.08
21
0.15
12
18
0.04
2.9
31
18
44
75 ,
79
58
66
:''
64
74
8
2
24
46
126
11
f
0.07
1.18
38
17
W v-l
sc M
10
•
12
; 11
a-
H U
O r->
3 &p
U 6
"*
i
^
i
T
X E
OnXJCTIVXT
cromhos/ci
O -ri
a 6
5050
3280
2060
3320
4230
4490
5020
'5720
6520
6520
6580
6750
7320
5990
5100
4540
5630
6070
5150
4720
5300
5780
t •
»
5880
5270
6440
5600
4480
5590
138
-------
APPENDIX A-4: page 5 of 6
DATE
11-4-70
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
1-1-70
2
3
4
5
6
7
'8
9
10
11
1*
E
,
X
a
8.8
7.8
7.0
7.0
6.9
7.0
7.1
7.6
7.5
7.6
7.8
7.2
7.5
7.3
7.7
8.0
8.0
8.1
8.5
8.8
8.7
8.1
8.5
8.1
8.5
8.6
8.9
9.0
9.1
9.2
9.1
9.1
9.2
9.0
9.0
8.9
9.1
9.4
8.8
9.5
9.3
9.2
8.8
7.6
7.6
8.0
8,2
8.3
8.5
8.8
9.0
9.0
8.9
8.8
9.0
9.4
9.4
8.7
8.7
8.6
8.6
8.8
8.7
8.4
7.6
7.8
7.8
7.9
- en
e s
S 5
M
d ***
i f
1130
655
420
280
250
300
350
410
420
470
495
470
525
520
525
575
560
550
675
675
550
395
480
525
490
560
700
660
680
730
705
930
915
930
860
840
775
825
990
900
820
840
840
830
650
575
575
575
680
850
88O
860
780
700
710
850
1025
535
760
775
875
950
840
740
500
425
380
330
,
s °
i ~
% %
OXYGEN
DEMAND,
fflg/1 02
§
1
1160
1350
864
1000
1020
1090
935
675
624
613
456
500
546
501
672
556
560
575
594
863
755
582
755
575
544
600
773
707
706
508
3
Sa ^
W "O
o in
s
245
276
-g
8£
H \O
J O
it
§g
Z -t
<-**
Bf
B
§5
S-*.
«
H I
Q tn
5 60
« t
NITROGENOUS
COMPONENTS,
mg/1 N
g
i
246
386
599
596
515
465
440
249
87
98
157
78
62
81
136
185
46
102
99
2.2
241
249
73
64
4.6
86
118
176
210
594
O w
ii
50
18
43
31
34
32
41
84
160
34
g
g
0.6
0.5
0.2
0.2
0.3
0.3
0.2
0.4
19
66
9.6
24
62
58
1.1
36
45
.2
.2
.4
.4
.4
.1
39 .
42
54
2.1
18
.4
4.0
|
i
0.01
0.01
•co.oi
<0.01
•oo.oi
0.01
<0.01
<0.01
<0.01
.07
-------
APPENDIX A-4: page 6 °f 6
DATE
1-12-71
13
14
15
16
17
18
19
20
3f
X
CU
6.8
7.3
7.5
7.8
8.0
8.1
8.2
ALKALINITY,
mg/1 CaCOj
250
375
470
600
640
525
625
|
O
s ^
u ep
OXYGEN
DEMAND,
mg/1 02
CHEMICAL
786
743
641
590
IOCHEMICAL
5-day
CQ
PHENOLICS ,
mg/1 C6H50H
CYANIDE,
mg/1 CH
THIOCYANATE
mg/1 SCN
SULFIDE,
mg/1 S
NITROGENOUS
COMPONENTS ,
mg/1 N
j
605
529
440
403
ORGANIC
NITROGEN
36
NITRITE
.3
.3
.3
.3
NITRATE
.24
.02
.04
.32
PHOSPHATE,
mg/1 P04
CHLORIDE ,
mg/1 Cl
-
!w B
CONDUCTIVTT
micromhos/CT
6840
6800
6160
140
-------
APPENDIX B-l:
BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS FROM COKE PLANT WASTES
ANALYTICAL AND OPERATIONAL DATA FOR THE CARBONACEOUS UNIT
DATE
2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
3-1-70
2
3
4
5
6
7
8
9
10
11
CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
nmiUD Ln
LIQUOR
ml/1500
gal.
J
**
22
n"<
2
^
LI
1 W
i— < U
X CO
3 Ou
.0 91
-H O
M •£•
TO BIOLOGICAL
pounds /day
QJ
C
O
4J
w
* CN
o °
t4
"Q D
OJ jj
> -rl
t-4 i— «
O '^
w 00
» E
•l-l
o
t£
ft *^
c: •*-*
3 w
o c
•a a
3 U
O >J
^ OJ
aa a
2
W
C
(0
Q
»!-*
(J
)
C/i
9 1/4
7 1/2
7 1/2
7
8
9
7
7
7
6
6
6 1/2
71/2
6
6 3/4
7
7 1/2
7 1/2
61/2
7 1/2
10 1/2
8 1/2
9
9 1/2
10
14
12
12 1/2
8 1/2
11
14
9 1/2
RETURN
SLUDGE
„
£ *
o
-------
APPENDIX:B-1; page 2 of 10
DATE
3-12-70
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
t\i Ifiwt xn
LIQUOR
ml /I 500
gal.
U
M
JS
a u
(Q *<3
O
£
750
1 0)
^4 i>
X <8
3 O.
.a w
i-l O
££
30
50
TO BIOLOGICAL
pounds/day
o
w
at
E
1
I
1
B
•H
,-)
4J
C
^1
3
ID
to
1J 4)
£4 *F-j
*O |^1
£
2
1/2
OJ
iJ
E§
3 O
*O ^
o m
w o
1
1
1
2
2
2
2
I
-
BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /min.
"c3
u
o ^
*4H i— <
O — '
j3 (•>
a
73.0
69.0
18.0
60.0
61.0
65.0
85.0
56.0
67.0
85.0
30.0
25.0
25.0
24.0
28.0
50.0
26.0
25.0
50.0
89.0
to
,— I
O
CO
"O fl)
lit 1J
•a TJ
C ^-t
a. u>
m £
3
en
e
-------
APPENDIX B-l: page 3 of 10
DATE
4-20-70
21
22
23
24
25
26
27
28
29
30
5-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
LIQUOR
ml/1500
gal.
J
*
*
) *O
• *H
1 «£
J
£
750
750
750
1 w
I— « u
>> a
»•§.
J3 01
-H O
H£
,•
100
125
125
50
100
125
125
TO BIOLOGICAL
REACTOR,
pounds /day
CU
C
o
w
CU
J
o
6
•H
rJ
4J
e
M
s
*t3
(U
q g
•0 J
£
u
u
CO
3 O
•H .0
TJ M
o rt
CAU
BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /min.
r-4
flj
U
[Q
W iH Id
W C O
-rl
r-l i-4
O "--
u) E
a
3.1
2.25
3.1
4.0
4.8
3.0
4.1
CD
C -^
O C
•a 41
3 u
O k
r-1 41
to a.
2
2
2
2
in
a»
•ill
c c
. Oj '-H
H
. a' u
O in
•M Q
EC
4-1 «r4
C J=
(U 0
E u
•r* CU
•Q c/1
0)
3 1/2
3
3
3
3 1/2
4
3
4
3
4
3
3
3
2 1/2
3 1/2
3
2 1/2
4
3
3
4 1/2
4
5 1/2
4 1/2
6
3
3
3
4
2 1/2
3
3 1/2
3
4
RETURN
SLUDGE
' *•
„
C V4
O a
•rl
O ^1
"2
w
262.0
412^6
740.0
400.0
400.0
250.0
325.0
600.0
600.0
623.0
725.0
785.0
300.0
400.0
350.0
Cfl
T3
O
to
T3 41
Q) 4J
•a .^
C ~H
41 ~~.
, a ^i
3
tn
SPECIAL
CONDITIONS
Q
U
jjj
kA
C
1
O
b
X
X
X
X
X
X
X
X
X
X
X
X
X
00
2*
•d
^
r-l
3
CO
01
I
p^
t/J
V
00
•o
_< (U
*W
00 "-<
c n
t-i CO
*J r-l
go
a.
X
X
OPERATIONAL NOTES
Reestablished 27. daily blowdown.
Sludge recycle, 0.9 gptn.
Waste flow off,
Haste flow off ? hrs.
Out of T.B.P.
Power off, 40 min.; Emergency air on.
Waste flow off.lO hrs.
Waste flow only, 0.5 gpm.
CO
-------
APPENDIX B-l: page 4 of 10
DATE
5-28-70
29
30
31
6-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
7-1-70
2
3
It
CHEMICAL ADDITIVES
TO EXCESS
AMMONTA
JWlVKllA
LIQUOR
ml /I 500
gal.
U
•
M
O tJ
.C i-t
0* U
01 ^Q
o
£
560
750
750
0
750
750
600
530
490
510
490
750
750
750
0
750
750
750
750
750
1 V
^•4 ^
^ J3
3 a.
^ CO
•ft O
^£
100
125
150
0
150
150
125
125
98
75
100
50
1OO
100
100
100
TO BIOLOGICAL
n^ Hf*mr\D
KEAL i UK ,
pounds /day
(U
o
4J
ID
i
E
T-l
tu
E
4
J* E
•S
15O.O
175.0
175.0
214.0
140.0
130.0
160.0
180.0
100.0
100.0
80.0
75.0
70.0
60.0
150.0
75.0
43.0
42.0
50.0
58.0
40.0
42.0
57.0
37.0
50.0
60.0
50.0
m
•o
O
k*
•0 T*
o — -
v> t>o
m c
0
3.0
3.1
3.0
2.1
2.25
0.2
2.4
2.7
2.7
2.0
1.5
3.1
1.4
•1.8
2.3
1.3
2.
1.8
5?
" -Q
C ^
0 C
•o 01
3 u
*-<
-------
APPENDIX B-l: page 5 of 10
DATE
7-5-70
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
8-1-70
2
3
4
5
6
7
8
9
10
11
12
CHEMICAL ADDITIVES
TO EXCESS
&MATWT&
aSfmfRJatA
LIQUOR
ml /1 500
gal.
s
'<5
-
750
75O
750
750
750
750
750
750
7 SO
750
750
750
750
750
750
750
«
,~i u
M
9 O.
s a
J J
H »•
100
100
100
100
100
100
100
150
100
100
150
150
150
150
150
150
TO BIOLOGICAL
REACTOR,
pounds/day
S
1
6
^ .
41
•U
C
3
»
•o
u
4J Q)
53
33
*»
E 8
35
D M
O 01
eno
BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /ntin.
*-«
U
>\ CM
o °
Vl
at 4j
o ^^
m t>o
43
O
3.0
1.8
2.0
1.9
2.0
2.6
2.3
2.7
2.7
2.0
2.1
2.5
2.4
2.6
0.1
2.2
2.0
1.5
1.9
2.3
1.8
0.8
2.3
2.4
1.4
1.9
&
»tj
•a at
S o
O Vl
^ 01
m a.
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
O
2
2
2
2
2
2
2
2
2
2
2
2
0)
4}
B C
^ ^
C u
o in
-r< -rt
*j a
0
•a
3 ^
(O -H
hA .-J
if I.
•** a
1"
X
X
X
X
X
OPERATIONAL NOTES
Waste feed off 2 hrs.
Waste feed off, 2 hrs.
Waste feed off, ? hrs.
Sludge recycle rate; 1 gpm.
Sludge recycle rate, .85 gpm.
Sludge recycle rate, .67 gpm.
-------
APPENDIX B-l: page 6 of 10
DATE
8-13-70
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
9-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
£U UrlUn Ln
LIQUOR
ml/1500
pal
gel .
y
•p4
O "0
«£• ^
£•«
B •<
O
J?
750
750
750
750
750
750
750
750
750
750
750
750
750
750
750
/
750
1 01
r-4 U
>> a
u ^
3 CL
J3 tO
•r4 O
M *£
E-i fc
150
150
150
150
150
100
100
150
100
150
150
150
150
200
200
200
TO BIOLOGICAL
REACTOR ,
pounds /day
01
c.
o
&J
m
fU
6
•H
,j
4)
J
4J
CJ
>4
3
«
•o
4J ^J
2 ^
T) >J
^
*
— i
d
u
at
(fl -H J-i
w c c
a) o 3
o g c
W -r4
& ^^
in oo
n S
«H
Q
2.1
2.5
.5
1.8
1.2
1.3
0.9
0.7
3.0
2.0
2.4
1.5
1.3
1.3
1.0
1.0
1.5
1.1
1.6
0.57
0.3
1.4
1.6
0.86
1.7
1.3
1.0
1.4
-1
c ^~
o c:
•a O
E o
•3 ni
•a to
CO
2 1/2
3
3
3
3
3
2 1/2
2 1/2
2
2
2
2
2
1 1/2
2
2
2
2
2
2
1 1/2
3
2
1
2
3
1 1/2
1 1/2
3
3
2
2 .
1
1
1
2
2
2
RETURN
SLUDGE
•*
s *
O Qi
O 4J
•H
H | ••^
o ^
•C E
e
M
250.0
123.0
170.0
209.0
250.0
200.0
218.0
200.0
233.0
200.0
327.0
407.0
250.0
180.0
210.0
180.0
•r*
0
•O Q)
0) U
C i~i
a) "--»
0. 00
01 E
3
CO
SPECIAL
CONDITIONS
H
o
4J
U
cfl
Q)
Cd
H
E
O
fe
X
X
X
X
X
X
X
X
X
00
C
•r-4
^
13
CO
• V
00
•o
3
t-4
cn
X
X
a)
"O
3 *j
.-( (U
en *F*
oo -^
c n
•H n)
So
pt*
OPERATIONAL NOTES
System off, 1 1/2 hrs.
Waste feed off,
Reduced aerator volume; on 707. waste.
Waste feed off, ? hrs.
Waste feed off, ? hrs.
Waste feed off, ? hrs.
Waste feed 70%.
Waste feed off ? hrs.
,
Waste feed off ? hrs.
Waste feed off ? hrs.
Waste feed off ? hrs.
Ammonia odor over aerator.
Waste feed off 1 hr.
Much less foam.
Waste feed off, 45 min.
-------
APPENDIX B-l: page 7 of 10
DATE
9-21-76
22
23
24
25
26
27
28
29
3O
10-1-70
2
3
4
5
6
7
8
9
ie
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
CHEMICAL ADDITIVES
TO EXCESS
LIQUOR
ml /1 500
gal.
1
1 *O
1 **^
i <;
»
*
750
750
75O
750
750
75O
750
750
750
750
750
AS
*^ fflj
J J3
3 O>
,fi. «0
•< O
ftfi
200
200
200
150
200
200
200
200
100
100
150
TO BIOLOGICAL
PPAPTflP
KtAv/ivJK ,
pounds /day
S
o
4J
n
g
E
i-t
»4
4)
a
n4
C
14
m
•o
0*
•U 0)
2 5
"O iJ
£
0)
„ 2
E C
3J
•o ^
O nt
BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals, /miiu
"«
u
n)
(fl *r4 ij
OB C 0
0) 0 3
O E D
e
o
^ 01
1 ni
S3
MIXED LIQUOR
Eu
01
9
4
0)
92
89
87
90
89
84
78
75
80
78
83
84
87
88
90
87
88
68
72
78
78
78
77
78
75
74
74
75
75
75
79
81
78
80
92
86
78
«•
c u
32
*M r*
o -•
£ E
S
100.0
65.0
30.0
21.0
8.0
7.0
14.0
4.0
0.6
3.0
1.0
4.0
3.5
4.0
1.2
1.5
2.5
10.0
13.0
.
•o
•H
O
cn
•S2
•O -ri
C f-t
oi 15
cn
640
760
G
0)
60
>» CM
o °
•O 0)
fr **4
^4 «— *
T3 T*
C r-4
at *^.
O. w)
3
CA
SPECIAL
CONDITIONS
o
u
01
on
c
1-1
Q
fa
X
X
X
X
t*
^
f-4
3
OQ
01
60
-o
3
r-4
tn
X
H)
•5 M
•-I 01
CO — <
l-l
•^•1 (f
4J r-l
go
(^
OPERATIONAL NOTES
Waste Feed Off, 45 rain.
Daily data sheet missing.
Waste feed off ? hrs.
Waste feed from 70% to 50%.
Affluent, very dark color.
Waste feed from 50% to 25.
Waste feed from 25% to 15%; reseeded
system.
olidg lighter color, waste feed
-------
APPENDIX B-l: page 8 of 10
DATE
29
: 30
31
11-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1-70
2
3
4
5
6
CHEMICAL ADDITIVES
TO EXCESS
LIQUOR
ml /1 500
: gal.
u
V*
to
(J T3
*G "»"*
o< o
to ^j
o
;?
04
750
750
750
750
750
750
750
750
750
750
1 O
i— 1 4J
•^t HJ
*•* £
3. 0.
J3 0}
•H O
E-r fo
150
150
150
150
150
150
150
150
150
150
TO ^ BIOLOGICAL
1 REACTOR ,
pounds/day
' 0)
c
o
u
. w
1>
3
•l-l
J
01
3
*H
i ^
4-1
C
M
m
•^3
V
u 4)
RJ I?
M f-l
t3 nJ
^
5S
4J
4J
0 C
3 O
•O h
O (8
CO U
BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /min.
^
cQ
U
3
«J
VI
01
o.
tH
71
71
70
75
73
67
67
64
69
75
80
78
72
73
73
78
71
67
61
69
75
75
75
74
78
72
62
65
75
78
79
80
79
80
91
90
89
90
90
d" b
O 0>
CJ -W
t4 (—4
43 ^^
o «-«
0
H
10.5
20.0
15.5
15.0
10.5
11.0
15.0
4.5
4.5
4.0
1.7
1.5
1.3
1.5
1.0
1.0
1.0
1.3
2.5
3.5
3.5
4.0
10.0
12.0
75.0
75.0
65.0
CO
M
01
>r^
t-»
be
e
280
220
100
140
I
5>\ CM
o °-
T3 V
d) *J
> •-*
o ^-
m bo
tfi G
a
1.3
2.4
2.3
2.5
6.6
2.6
3.3
2.7
1.6
2.2
1.8
1.94
1.2
3.0
2.6
2.4
2.O
2.7
2.8
2.5
4.3
1.4
2.9
2.6
2.6
2.6
2.4
2.3
2.0
3.1
3.1
« -o
d ^.
3 u
0 d
•a at
3 u
O M
t-* a>
to a
'
v>
01
IS
C u
O to
•H- -i-(
<6
C X
a) u
e o
•H 4)
•X3 C/3
Q)
Cfl
2
2
2 1/2
1 3/4
2 1/2
3
2 1/2
2
2
2
2
1 1/2
1 1/2
2
2
1 1/2
2
2
2
2
3
3
3 1/2
3
4
3
3
4
4
4
4
4 '
3 1/2
9
3
4
3
RETURN
SLUDGE
„
d ^
o o>
.
ii | |
IW *^.
O ~*
£ e
^|
15.0
20.0
22.0
21.0
10.0
15.0
9.0
3.0
1.6
1.0
15.0
1.0
1.0
1.1
3.0
10.5
5.5
5.0
5.0
11.0
80.0
130.0
tn
•a
o
c/5
"O nl
01 W
d ,-<
41 ~^.
O- 00
w ^
3
CO
SPECIAL
CONDITIONS
M
U
-------
APPENDIX- B-l: page 9 of 10 "
DATE
12-7-70
8
9
1O
11
12
13
14
15
16
17
18
W
20
21
22
23
24
25
26
27
28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11
12
13
14
CHEMICAL ADDITIVES
TO EXCESS
LIQUOR
ml /I 500
gal.
"^
. u
750
750
750
750
750
750
750
750
750
750
01
r*i *J
»* ti
3 O.
.a m
•^ o
E-i tt<
150
150
150
150
150
150
150
150
TO BIOLOGICAL
OPA/^rP/M3 '
K£i At> i UK ,
pounds /day
OJ
c
o
01
0)
e
•H
J
0)
3
1-1
pJ
U
C
M
3
CO
"O
0)
4J a
CQ E
M -r1
•Si"
X
cu
4-1
fd
E c
D 0
•H JJ
•a M
o «
VJ O
BIOLOGICAL REACTOR
INFLUENT
FLOW RATES
gals. /tnin.
F—4
(fl
y
(U
01 'ft |ri
W C O
0) O 3
o i u
w< ^
c
o
•l-f M
4-> 0)
r-l fl)
0
MIXED LIQUOR
fa
o
0)
^i
3
a
M
a>
H
87
88
88
87
91
92
91
91
89
92
86
85
85
84
82
84
90
88
93
90
86
83
88
88
88
87
86
90
95
97
95
95
96
87
85
84
85
86
"r^
o ^^
ta &p
w g
•H
a
3.3
4.1
4.1
1.6
2.3
1.8
2.4
2.6
.86
2.0
1.9
2.3
2.3
1.8
1.8
2.3
1.8
1.7
2.3
1.8
1.9
2.4
1.7
1.9
3.1
S"
** *o
c -^.
9 u
o c
"O O)
0 U
pa o.
tn
(U
G S •
u
(0
•H
o
ip4
f-t
CJ
a)
en
3
4 1/2
3 1/2
3 1/2
31/2
3 1/2
3
3
2 1/2
2 1/2
3
3
3
3 1/2
3 1/2
3
3
3
3
3
3
3
3
3
21/2
3
2 1/2
3
2
2
3
2
2
2
2
2
RETURN
SLUDGE
„
C M
o W ***
r
78
150.0
250.0
275.0
425.0
250.0
250.0
540.0
450.0
400.0
3OO.O
400.0
225.0
350.0
400.0
350.0
375.0
350.0
450.0
450.0
350.0
450.0
440.0
430.0
593.0
450.0
425.0
408.0
725.0
in
.-*
O
TJ at
a u
TJ -r4
C r-4
3) •"»*
ft?
SPECIAL
CONDITIONS
O
u
(0
01
fV*
00
™
•rH
1
X
X
X
X
X
S
j;
3
EQ
01
r\H
•D
X
X
X
X
at
00
P M
,-< at
m
bO *H
& Lj
•rW C3
^1 r^
(B O
O
«— 1
OPERATIONAL NOTES
Waste feed now 50%.
Waste feed off, ? hrs.
Waste feed off, ^ hrs.
"
Waste feed now 25%,
Waste feed off, ? hrs.
Jaste feed now 35%.
Waste feed off,
Waste feed off,
aste feed now 50%.
Waste feed off,
aste feed reduced intermittently.
VO
-------
APPENDIX B-l: page 10 of 1O
DATE
1-15-71
16
17
18
CHEMICAL ADDITIVES
TO EXCESS
AMMONIA
LIQUOR
ml/1500
gal.
Phosphoric
Acid
750
Trlbutyl-
Phosphate
150
TO BIOLOGICAL
pounds /day
Limestone
*•
la
c
i
Hydrated
Lime
Sodium
Carbonate
-
BIOLOGICAL REACTOR
INFLUENT
gals. /min.
Excess
Ammoniacal
Liquor
-
Dilution
Water
MIXED LIQUOR
O
V
3
a
!
H
86
90
89
89
i'- '
Imhoff Cone,
ml/liter
250.O
270.0
ra
>u
•H
Suspended So
mg/liter
G
0)
Dissolved Ox
mg/liter 0
Bloudoun,
percent/day
(0
V
.£
CD -rt
C 0
O 01
Sedimentati
Secchi Di
2 1/2
3
2
2
RETURN
SLUDGE
^
Imhoff Cone
ml/liter
450.0
490.0
-------
APPENDIX B-2: BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS RROM COKE PLANT WASTES
Analytical and Operational Data for the Nitrification Unit
DATE
2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
BIOLOGICAL REACTOR
Influent
low Rates
gpm
$ I
0 C
M
1
o
1
CHEMICAL ADDITIVES
Daily Dosage
Pounds
1 S
•*•* tfl
§ tn
s
s
I
J
i
2
2
1
1
3
2
2
2
«
j
c
3
ta
1
1/2
1 1/2
- 1/2
2 I/
2 I/
2
2
2
2
2
4
4
4
4
-o
e
(B 01
* i
^ »*
x
3
3
IS
— o
0
llliltters
u
5^
P
L,
S.5
a Q.
3 B)
HO.
Sodium Hydroxide
Feed Solution
Volumetric
Composition
o .
S ~i
S
? a
3
s a
•o -t
V **
v e
[X
MIXED LIQUOR
u,
41
t-i
i
^
t
H
90
78
72
75
92
85
80
84
81
77
80
83
77
82
85
76
78
81
84
82
80
80
73
82
90
80
82
X
o.
6.6
7.0
6.7
7.2
6.8
7.7
7.5
6.9
6.9
6.7
6.6
7.3
7.2
7.3.
7,4
6.9
7.2
9.6
6.8
6.9
7.1
6.8
7.0
7.2
6.4
>, (^
c n
J£ ' —
< S?
119
102
63
95
55
150
126
86
111
123
127
205
178
174
138
135
166
130
125
140
115
120
170
174
90
0*
•a ^.
1 =
in a*
o
u
c
O f
o u
0 -~
"
10.0
4.0
3.0
2.5
5.0
4.5
4.0
10.0
5.5
5.0
5.0
3.5
5.5
4.9
5.0
6.0
7.5
9.O
9.0
8.5
t
IS
U
c
-
«
X
y
u
(Q
4
4 1/4
3 1/2
3
4
4
31/2
3
3 1/2
3 1/2
4
3 1/2
4 1/2
4
3:1/2
4 1/2
5 1/2
6
4 1/2
4 1/2
5
Return
Sludge
Is
o ~~
% "e
0.75
7.0
11.0
12.0
8.0
10.1
10.0
17.0
15.0
13.0
19.0
25.0
22.0
15.0
t
Special
Conditions
u
o
1
f
£
no
S
S
ta
V
W)
w
M
"O
3 n
»3
NJ id
Sy
OPERATIONAL NOTES
Sludge recycle 1 gpm.
Reactor off 45 min.
Attempting to maintain PhS.alk-
200
Sludge return problem
Rising sludge noted during Imhoff
cone test
Mixer and air off, ? hrs.
-------
APPENDIX B-2:
page 2 of 12
Ui
to
DATE
28
3-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
4-1
2
Influent
Flow Rates
gpm
3
S *j
asg
1* -
<0«
3
u
k
I
^
b 1/2
J
i 1/2
)
5 1/2
21/2
3
>
1/2
L
1/2
1/2
1/2
L
1/2
1/2
t 1/2
1/2
; 1/3
) 1/2
L 1/2
1/2
" 1/2
1/2
1/2
Hllliliters
u
iL
r
~r4 O
£•< a.
Sodium Hydroxide
Feed Solution
Volumetric
Composition
g .
g
•n
2250
V «-"
u tg
S"
30
Of
S |
£ •
MIXED LIQUOE
u.
*
01
3
01
t*
85
87
84
87
84
84
82
80
81
84
84
78
74
79
80
83
82
79
88
8O
80
70
83
83
87
81
81
86
81
83
86
88
75
O.
7.1
7.0
6.9
6.8
7.3
7.5
7.6
7.2
7.1
7.2
7.7
7.0
7.1
7.2
7.5
7.5
6.7
6.6
6.9
7.0
7.1
7.8
7.3
70
7.2
7.0
6.9
7.2
7.1
7.1
7.2
7.1
6.7
£" 51
a —i
1 t
123
117
103
75
16O
162
193
154
145
153
146
12O
no
105
158
147
108
118
98
127
145
162
ISO
103
113
92
93
145
160
139
148
170
105
(M
o
Jnli
•o *•*
Is
••< Ml
o >•
'
0)
c
O k*
U V
P
8.0
7.5
7.O
8.O
9.0
9.0
16.0
18.0
15.0
21.O
24.0
2.0
21.0
25.0
a
•O
O
T,
|f
(0
•si
a u
c
O "
4J 00
a -H
li
0) 0)
in tn
6
51/2
6
6
8
8 1/2
10
8
9
10
7
8
9
7
9
.O 1/2
.0
9 1/2
8
4 1/2
6
7
7
5
6
6
5
5 1/2
5
5 1/2
6 1/2
Return
Sludge
*
o ».
|C
3-
18.0
40.0
24.O
23.0
23.0
20. 0
36.0
52.0
33.0
44.0
45.0
43.0
47.0
66.0
•
-
u?
•o
1 *
1
Special
Coo**1 *•*«•««
L>
o
g
1
S
-r<
.K
n
9
3
«
0
3 U
to ^i
g"*
i-J 0>
E
OPERATIONAL NOTES
Recycle pump off, ? hrs.
-------
APPENDIX »-2: page 3 of 12
in
lo
DATE
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
2O
21
22
23
24
25
26
27
28
29
3O
5-1
2
BIOLOGICAL REACTOR
Influent
Flon Rates
SP™
u c
•a
Off
ta
V
3
i
l
i
1
CHEMICAL ADDITIVES
Daily Dosage
Pounds
is
IS
P
12
12
12
12
o
I. limit
I
•rl
•1
e
b
"g
||
E •
Sodlui
Carbonj
2
1
2
2
2
2
2
2
2
2
2
2
2
ll/
4
lllillters
i
>
150
ISO
^ tt
s-s.
.0 (B
HI
4
6
None
6
3
3
3
2
2
2
4
4
5
7
Sodium Hydroxide
Feed Solution
Volunetric
Composition
-
K~m
g
m
4000
45OO
50OO
3OOO
40OO
50OO
60OO
7OOO
50OO
7OOO
7000
7000
85OO
10OOO
125OO
5000
20000
17500
18OOO
18OOO
1800O
18500
18500
••j
« w
40
40
40
40
40
40
40
40
40
40
40
30
4O
40
40
4O
40
40
40
40
40
at
*j
M C
f 5
1 •
100
75
70
110
110
9O
MIXED LIQUOR
it.
\
0
H
H
81
82
95
84
85
85
88
88
90
88
90
92
93
93
90
89
90
93
94
94
94
94
94
95
97
97
90
84
S
7.2
6.9
7.3
8.1
6.8
6.6
6.4
6.8
7.2
6.5
6.2
7.3
7.1
7.5
6.9
6.9
6.9
7.3
7.3
7.4
6.7
7.4
7.0
7.8
7.5
7.4
7.1
7.4
£ ff
2 "i
•*« U
h
120
80
85
230
65
25
35
70
60
45
5O
77
85
170
57
77
6O
100
150
160
55
105
100
160
163
197
90
20O
(Nt
0
TJ *^
o -
« c
« «l
ss
3
~*
£
P
28.0
38.0
30.0
22.0
26.0
38.0
20.O
20.0
25.0
26.0
31.0
24.0
22.0
26.0
25.0
•0
^
O
w
•0
01
640
380
830
6 1/2
5
5
4
8 1/2
9
9
7
9
8
5 1/2
4
41/2
6
5
5
5
5
5
4 1/2
5
4
5
4
4
Return
Sludge
e
P
52.0
62.0
72.0
55.0
51.0
27.0
58.0
75.0
38.0
50.0
34.0
75.0
30.0
M
•a
2
in
•a
0) r-t
C 00
g. f
Ul
Special
Condition
n
o
i
2
1
X
X
X
X
X
X
X
X
X
je
1
01
s§
3
CO
s
BO
3 *•
VJ -rf
I* 2
g"
fid
X
X
OPERATIONAL NOTES
Temperature, 95°
Recycle pump off, 1 hrs.
Flow off NaOH, ? hrs.
Recycle pumps off, ? hrs.
recycle pump off, ? hrs.
-------
APPENDIX 8-2: Page 4 Of 12
DATE
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27 ;
28
29 •.
BIOLOGICAL REACTOR
Influent
Flow Rates
gpn
jj
tj c
C 3
U
1
1
-
I*
«
S
1
1
1
CHEMICAL ADDITIVES
Daily Dosage
Pounds
§v
u
"c *
g 3
E tn
16
24
24
24
20
24
24
24
24
24
24
24
8
C
o
E
, ]
0)
3
c
3
co
_
E
0 -
u c
S S
X
o
68
3.0
3.1
3.1
4.6
3.0
5.3
3.1
3.1
3.1
i „
O tt*
4J
l*J -rt
.gS
E S
12.0
15.0
15.0
11.0
1.5
7.5
11.0
7.0
3.0
5.0
5.0
3.5
3.5
4.5
4.0
4.0
3.5
5.0
5.5
4.5
^^
«.
570
510
610
280
350
428
70
90
200
M
.s
-
s
^
r?
U
01 01
vi tn
3 1/2
31/2
6
5
4
4 1/2
4 1/2
7
4 1/2
5
6
7
5
5
4
6 1/2
9
11
15
11
6
10
4
4
Return
Sludge
cj w
H4 -rt
u* ~*
O ^
$ 6
25.0
25.0
19.0
10.2
15.0
17.0
6.5
7.0
7.0
20.0
4.5
8.0
16.0
tn
•a
Z*
en
•a
-S ^
C M
o) e
3
Special
Conditions
^
u
i
00
c
g
«
r?
Si
X
X
X
X
X
00
e
3
co
on
•o
J2
X
(U
-5?
^
» t
-rt IB
0) U
£
OPERATIONAL NOTES
Out of T.B.P.
Intermittent caustic addition
Recy cle pump of f , 1 hrs .
Power off, 40 min, emergency air
on
In t e rmi 1 1 en t c-aus tic addition
Intermittent caustic addition
Ol
-------
APPENDIX B-2: page 5 of 12
DATE
30
31
6-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
BIOLOGICAL REACTOR
Influent
low Rates
gpm
iarbonacec
Unit
Effluent
»4
V
$
1
CHEMICAL ADDITIVES
Daily Dosage
Pounds
Anno ni am
Sulfate
24
24
24
12
12
12
12
12
12
12
16
8
8
12
12
20
24
24
24
24
24
24
24
24
24
24
24
24
24
Limestone
%
~S
»j
u
c
V
Hydrated
Line
Sodium
Carbonate
4
2
2
2
2
4
3
3
2
4
2
2
2
2
2
2
2
2
2
2
2
2
2
2
llHHters
u
Phoaphori
Acid
150
150
150
200
200
200
2OO
200
200
200
2OO
2OO
200
20O
200
200
200
200
200
200
20O
200
200
2OO
Trlbuytl
Phosphate
Sodium Hydroxide
Peed Solution
Volumetric
Composition
X
O '
Se
g
U*l
40OO
7000
9000
1500
9OOO
1500
12000
1000
10000
2000
13OOO
15000
M •
W ~*
.3
40
40
40
20
40
40
40
40
V
!l
£ •
Yes
Yes
Yes
None
50
Yes
Yes
100
100
100
50
75
75
75
75
90
100
HIXED LIQUOR
b.
«
T3
u
a
t.
V
!
93
90
89
85
87
90
87
92
92
91
91
93
95
95
95
96
95
96
93
93
95
95
95
97
94
95
93
94
95
96
95
s
8.0
8.0
7.8
7.9
8.3
7.9
7.6
8.0
8.7
8.1
7.9
7.6
7.4
7.4
6.8
7.1
6.5
6.9
6.5
7.4
7.1
7.0
6.4
6.7
7.2
7.1
6.7
6.9
7.2
7.4
7.8
>. C"l
Alkalinlt
mg/1 CaCC
290
350
190
175
240
240
2OO
2OO
225
2OO
170
103
112
83
35
80
25
37
50
83
- 33
48
20
45
77
100
45
1OO
90
105
66
c?
•o -••.
* »
> £
1 c
m tt
s!
3.1
3.1
3.0
3.0
2
2.0
3.0
2.4
2.9
3.2
3.0
3.3
2.9
2.9
2.3
3.7
w
c
Imhoff Cc
ml/lltei
6.0
7.0
5.0
4.0
2.5
2.0
1.6
1.2
1.4
1.7
1.5
5.0
2.0
3.5
2.0
2.0
2.0
1.5
2.5
1.75
2.0
2.5
n
^
^
o ,
V)
•o
•o-—
|r
9
cn
il
-------
APPENDIX B-2: page 6 of 12
DATE
7-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
BIOLOGICAL REACTOR
Influent
Flow Rates
gpm
i
h!
j> = C
3 S
1/4
1/2
V
3
3/4
1/2
1
CHEMICAL ADDITIVES
Daily Dosage
Pounds
1 2
E u)
24
24
24
24
24
24
24
16
16
12
C
o
e
fc
1 =
tfk V)
Q S
2.4
2.7
2.5
3.1
1.8
2.1
2.0
2.4
2.0
2.9
3.1
2.3
2.7
2.6
2.3
2.7
2.9
2.1
3.0
3.6
3.3
2.9
3.5
3.1
-------
APPENDIX >-2:~ page 7 of 12
.
DATE
8-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
BIOlOCICAl REACTOR
Influent
Flow Rates
gpm
u
0 =
u
0.25
a
fQ
^
0.9
0.88
0.7
CHEMICAL ADDITIVES
Daily Dosage
Pounds
E V
-3 «
O —i
j*
12
12
12
12
12
12
12
12
12
12
12
8
8
12
12
12
12
12
12
c
o
«
-5
>j
c
3
oa
•o
01
Qt Ol
|3
2
§ §
TJ .0
0 t.
U
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
illlliters
u
^
: -o
o. *•
at u
3 <
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
-* tJ
J 0)
3 Q.
rl O
-i B.
Sodium Hydroxide
Feed Solution
Volumetric
Composition
1-
ya E
in
5000
kl •
0) •-<
« 00
40
2
tf C
Tj •£
Ol r*
None
None
None
Yes
35
None
None
None
None
None
125
Yes
None
None
None
MIXED LIQUOR
k.
a
»*
^
IB
^
H
96
97
97
97
96
95
95
95
95
95
98
93
94
97
98
96
96
96
90
94
98
98
98
96
94
92
94
92
X
p.
8.0
7.7
7.4
6.9
6.8
6.4
6.8
6.7
6.7
6.6
6.5
7.0
6.7
6.6
6.7
6.6
6.6
6.4
6.3
8.7
8.5
8.4
8.6
8.2
8.0
7.8
7.8
>> £»
u O
"-1 U
T* O
01 ,-1
5 t
175
120
80
50
43
24
75
45
45
20
55
78
30
40
15
20
15
75
20
420
245
205
200
275
205
265
150
r-j
O
TJ -*.
S V
> 1=
1 5
-*J 00
Ql
3.3
2.9
3.0
4.0
3.1
1.8
1.2
1.8
2.2
1.8
2.1
2.2
1.6
2.7
2.6
V
e
3 S
*j
o *^
.E r-t
M ^
2.5
2.5
2.1
2.0
5.2
1.2
1.2
1.0
2.0
0.9
1.0
1.25
2.5
-o
•H
£
X)
•O ^^
C 00
1
3
in
*!
o
-
§
ft
o
o
to
8
8
10
12
11
13
13
3
10
10
10
3
12
14
14
15
31
29
5
4
4
6
7
7
6
Return
Sludge
c
O M
O a
iw ^j
IS
M
5.0
5.0
5.5
3.0
5.2
3.3
2.0
3.5
209.0
2.1
3.0
2.5
2.0
•o
-
V)
•o C
C tf)
s. *
ta
VI
Special
Conditions
^
o
u
J
W)
•-
0
£
i
Of
00
tJ
3
to
01
00
13
3 *•<
e S
iH
-------
APPENDIX B-2: page 8 of 12
DATE
29
30
31
9-1
2
3
4
5-
6
7
8
9
1O
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
BIOLOGICAL REACTOR
Influent
Flow Rates
gpm
•
3
8 w
1 Carbonac
Unit
Effluen
O
0
0
0.25
0.25
v
u
o
u
Daily Dosage
Pounds
E «
Amnoniu
'" Sulfat
S
S
I
S
€
-J
S
m
•0
01
II
x"^
4)
1 Sodium
| Carbona
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
MlUiliters
u
b
Is
r
4J
Trlbuyt
Phospha
20
20
20
20
20
20
20
Sodium Hydroxide
Peed Solution
Volumetric
Composition
X
O -
st
g
in
60OO
90OO
12OOO
750O
9000
6OOO
6000
9000
9OOO
9OOO
9000
9OOO
900O
9000
9000
9000
9OOO
9000
9000
10000
10OOO
10OOO
10OOO
10OOO
10000
10000
9OOO
tJ -
« ~d
4J (g
.-
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
V
u
2 |
•o ---
I •
None
None
120
125
50
35
125
160
125
150
155
160
155
155
140
140
135
150
150
155
155
140
150
160
155
150
150
HIKED LIQUOR
b.
*
• u
V.
3
w
i
|
93
94
95
93
90
94
95
94
94
97
93
93
95
94
94
94
95
97
93
98
95
96
97
94
95
92
95
93
90
84
85
3:
a.
7.3
6.7
6.7
6.5
6.1
6.7
7.0
6.8
6.3
8.3
7.0
6.6
7.0
7.2
7.3
7.2
7.3
7.4
7.5
7.2
6.9
6.9
6.9
7.0
7.0
7.8
7.0
7.0
7.0
7.1
7.5
4J Q
•M U
5 3
S Z.
3 S
80
30
20
25
45
45
65
40
35
195
60
50
80
90
88
88
125
115
165
9O
72
80
8O
90
80
165
80
80
80
80
130
o
;
•o *^
s »
> £
.-<
i Disso
1 Oxygen,
3.5
1.3
1.0
3.0
1.9
2.2
2.9
1.4
1.8
2.2
2.2
2.0
2.3
2.1
2.8
2.4
2.2
2.3
2.7
-------
APPENDIX B-2: page 9 of 12
DATE
30
10-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
BIOLOGICAL, REACTOR
Influent
low Rates
gpm
u
C 3
In
HI
li
% fi
« S
ft (J
M ' — .
180
110
70
60
45
65
65
140
80
55
50
40
55
40
47
57
45
43
55
50
130
185
520
65
75
90
130
80
57
111
LIQUOR
o"
-o —
.*
O "
u) c
S S
S
2.6
2.2
2.1
2.7
4.1
2.8
2.4
2.7
3.1
30
3.8
3.7
2.8
2.4
S
(S V
w
1*4 ~4
O ^
20.0
10.0
20.0
11.0
30.0
23.0
24.0
25.0
15.0
15.5
15.5
35.0
13.0
25.0
10.0
12.0
10.5
10.0
13.0
^
op
E
H
H
C
°
u
a
u
"5
u>
6
5
5
4
4
6
6
6
8
5
6
6
6
6
6
6
6
7
7 I/:
7
6
6
6
6
Return
Sludge
o u
u e
lu ii
"E ~e
"
26
26
25
60
10
30
30
50
40.0
24.0
20.0
2.5
35.0
"D
Z!
•o
•o •--
C M
» e
a.
09
3
m
Special
Condlt Ions
h
o
1
Sf
c
g
^
00
f?
i
QJ
3
U)
01
00
•o
- s
W) t*
•5 «
U -J
« U
O
b*
OPERATIONAL NOTES
Waste feed off, ? hrs.
Waste feed off, ? hrs.
Waste feed off, ? hrs.
Note high ph caused by low Ph 0
Inte rmittent caust ic
Ui
VO
-------
APPBHDIX B-2: page 10 of 12
DATE
30
31
11-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
2O
21
22
23
24
25
26
27
28
29
30
Influent
Flow Rates
SP"
1 .
1 Carbonic
Unit
1 Ef f lu»n
0
BIOLOGICAL REACTOR
CHEMICAL ADDITIVES
Daily- Dosage
Founds
E •
3 u
E en
6
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
12
12
8
12
12
12
12
12
f
9
12
12
12
12
12
tt
c
Limtito
*
c
on
-o
u
„
Sodium
Carbona
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Kiililiters
o
f1
-_« AJ
1 Trlbuyt!
Phoiphai
Sodium Hydroxide
Feed Solution
Volinsetric
Composition
50% NaOH
ml.
9000
12000
135OO
13500
3000
3000
3000
3000
30OO
3000
3000
3000
20OO
3000
450O
5OOO
7OOO
9OOO
9OOO
9OOO
3000
60OO
7500
12000
7OOO
I8
45
40
40
40
50
40
40
4O
40
40
30
40
40
40
45
45
45
45
22
4O
40
45
V
a C
1 •
110
115
None
None
100
100
100
100
80
8O
150
150
125
150
150
150
150
150
None
100
75
75
75
ISO
b.
|
V
81
80
83
83
76
77
76
76
83
88
86
81
82
81
83
82
77
74
SO
83
85
83
83
88
83
73
75
85
80
87
89
83
3:
a
7.3
6.7
6.7
6.9
9.4
8.8
8.4
8.1
7.5
7.O
6.8
7.O
7.0
7.1
7.0
7.1
7.1
7.4
7.O
6.8
6.6
6.7
6.8
6.8
7.1
7.7
6.7
6.9
6.8
6.5
6.7
7.0
^8
C •*
-v* O
« «-•
Jf ""»•
167
55
55
63
960
565
380
225
110
55
50
65
58
67
55
47
63
97
6O
50
33
37
4O
42
65
17O
35
47
37
27
37
70
o
•s"
Dl»o
Oxygen,
2.4
2.0
2.6
7.2
3.8
3.9
3.4
3.4
3.3
3.9
3.1
4.5
2.8
3.7
2.9
3.1
2.4
3.2
2.9
2.8
3.2
3.1
3.6
3.0
3.4
O »*
1
20.O
5.0
5.0
5.O
4.5
4.O
4.5
5.0
5.0
4.0
4.O
3.0
5.3
4.5
_,
?
•sl
TJ
e
w •
2S
c
V •*«
e.c
ta m
7
8
8
7
8
7
5
8
7
8
8
8 1/2
7
9
9
9
7
7
7
8
9
9
10
1O
1O
10
10
9
9
9
Return
Sludge
Is
It* VJ
O "•••
£ ^
15.5
10.0
18.0
15.0
5.5
5.5
10.0
8.3
8.0
5.6
5.4
1O.O
10.0
5.2
10.0
rt.
£
Special
Con** *•"*•""*
^
o
1
I
X
3
1
in
1
V
«D
jj jj
»s
|3
OPERATIONAL NOTES
Waste feed off, ? hrs.
Waste feed off, ? hrs.
Waste feed off, ? hrs.
Aerator off, 1 hrs.
-------
APPENDIX 1-2: page 11 of 12
DATE
12-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
BIOLOGICAL REACTOR
Influent
low Bates
gpm
Carbonaceous
Unit
Effluent
M
V
S
CHEMICAL ADDITIVES
Daily Dosage
Pounds
Amnonium
Sulfate
12
12
12
12
12
12
12
12
3
.
Limestone
1
4t
a
IK
Hydrated
Lime
Sodium
Carbonate
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
llliliters
Phosphoric
Acid
Tribuytl
Phosphate
Sodium Hydroxide
Feed Solution
Volumetric
Composition
5O7. NaOH
ml.
8000
10000
10000
10000
12000
10000
1OOOO
10500
11000
11000
11000
3000
7000
7500
7000
7000
3000
3000
4OOO
7500
9500
9500
75OO
8500
9000
•4 .
V —
ss
45
45
45
45
40
40
40
45
45
40
40
40
45
45
40
40
45
45
45
45
45
45
60
50
45
ai
*j
fl
£*
150
150
150
120
125
140
140
150
150
150
13O
130
150
150
150
150
150
150
. 150
150
150
160
180'
150
150
MIXED LIQUOR
b.
Temperature *
88
9O
91
88
87
88
81
84
86
86
88
78
78
78
81
84
83
88
SS
88
84
88
80
82
75
78
£
6.8
6.8
7.0
6.7
6.8
6.9
7.2
6.8
6.8
6.9
6.9
6.4
6.8
6.9
7.2
6.9
9.4
6.9
6.8
6.8
6.8
6.8
7.4
7.1
7.7
7.1
Alkalinity,
1 mg/1 CaCOj
45
43
65
50
53
57
102
57
57
70
75
190
57
65
88
60
500
52
47
47
50
47
120
80
167
78
(M
O
Dissolved
Oxygen, nig/1
2.8
3.0
1.8
3.1
2.9
2.5
4.8
4.6
2.5
2.7
, 2.7
3.0
3.0
2.9
3.3
3.0
3.0
2.4
2.8
2.9
2.8
2.9
Imhoff Cone
ml/liter
4.0
4.5
2.5
4.0
4.2
4.5
5.5
5.5
5.5
4.0
4.0
4.0
3.5
4.5
4.0
5.5
3.5
4.5
5.5
in
•O
Z3
Suspended Sc
mgA
220
480
370
160
Z£
g*
1.:
Sedlmentat'
Secchi Dlsi
9
19
20
12
13
11
11
17
15
11
11
10
8
8
10
10
10
10
10
9
9
9
9
10
9
9
Return
Sludge
u
Imhoff Com
ml /liter
17.0
5.5
5.2
10.0
8.0
8.0
5.0
4.5
5.0
8.0
10.0
10
•0
A
Suspended S<
mg/1
Special
Conditions
i«
o
(j
I
1
-^
jt
1
w
3
V)
9
00
1 >.
Floating SI
Clarlfl<
OPERATIONAL NOTES
Waste feed off, ? hrs.
Recycle pump off, ? hrs.
Waste feed off, ? hrs.
Waste feed off, ? hrs.
Waste feed off, 6 1/2 hrs.
Waste feed off, ? hrs.
Sludge return problem
Waste feed off, ? hrs.
-------
APPENDIX B-2: page 12 of 12
DATE
28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11
12
13
• 14
15
16
17
18
BIOLOGICAL REACTOR
Influent
Plow Rates
gpm
A
S *j
O p 1-4
t £
o
-
s
, CHEMICAL ADDITIVES
DaLly Dosage
Pounds
12
i "3
!«
s
i
s
J
s
B
c
3,
-0
S I
£-•
flj
i s
? E
"3
2
2
2
2
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
Milliliters
w
s
e '
QJ
>v J^
3 a.
££
Sodium Hydroxide
Feed Solution
Volumetric
Composition
3.
Si
g
9500
10000
10000
60OO
6000
7000
9000
8000
6OOO
3000
4000
4000
4000
5000
6OOO
B-
a to
45
45
45
4S
45
40
45
45
40
40
50
40
40
45
45
at
,3 c
E
•o **.
1 =
150
150
150
150
150
145
150
125
145
None
130
150
150
150
150
150
MIXED LIQUOR
Ft.
01
w
H
H
83
86
83
80
78
80
86
82
76
74
74
74
75
83
84
85
91
92
91
85
84
84
£
6.9
7.2
7.0
7.2
6.9
6.9
6.7
7.1
7.0
7.1
6.7
7.3
8.0
8.0
7.4
7.4
7.0
7.0
7.2
7.1
7.3
7.2
£ -
1 I
•** O
ttt — 1
S "i
58
75
85
98
53
53
45
80
80
80
40
90
225
205
77
125
25
70
83
70
85
70
o"
<<=
O -
3 S
g
2.6
2.6
2.9
2.4
2.9
2.4
2.8
3.7
ei
C
5 S
O --
3^
7.0
5.5
6.8
7.0'
5.5
4.5
5.0
5.5
5.0
4.5
3.0
4.5
4.5
5.0
5.0
4.5
•o
'£
-o
1^.
10
in
ll
H j:
c
0 -
n TJ
0) t4
e £
TJ y
01 (1)
9
8
10
9
10
10
9
8
7
7
6
4
6
2
8
21/2
7
6
7
6 1/2
Return
S LodKe
ss
ss
jj-i
8.0
9.0
6.1
29.0
8.0
5.0
8.0
8.5
7.5
5.5
7.0
•o
£
•o
C WD
o. B
(a
CO
Special
Conditions
«
' c?-
1
4)
00
•c
VI
V
00
1 s
c ~*
i 3
0
OPERATIOSAL NOTES
-
o\
to
-------
APPENDIX B-3:
BIOLOGICAL REMOVAL OF CARBON AND NITROGEN COMPOUNDS FROM COKE PLANT WASTES
Analytical and Operational Data for the Denltrificatlon Unit
DATE
2-1-70
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
3-1
2
3
4
5
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm
Jj
(U
< *J 3
f* *JLJ
; °u
z
1
w
ft)
5
Additives ,
Working Solutions
• n
fl) C
M a.
4.6
2.3
3.5
(U
to to
5
4 1/4
3 1/2
3 1/4
5
3 1/2
3
3
3
2 1/2
2 1/2
3 3/4
5
7
5
4 1/2
4
4
3
3 1/2
4
3 1/4
31/2
3 1/2
4
4
RETURN
SLUDGE
4
•*
"5
4-4 ^4
O "^-
•§ B
M
30.0
40.0
40.0
40.0
40.0
40.0
40. 0
40.0
40.0
40.0
40.0
40.0
40.0
40.0
40.0
15.0
13.0
9.0
•O U)
C -D
to o
3 to
to
SPECIAL
CONDITIONS
op w
-.4 *J
E u
g 3
. g
00 -H
*O Ji
S 3
0)
44
oo a
B -4
a at
£ IS
to
X
X
OPERATIONAL NOTES
Added 20 Ibs. of sewage sludge to
reactor sludge recycle 1 gpm.
Recycle pump problem
Sugar concen trat ion reduced
2% blow down initiated, to cont. on daily
basis
-
Recycle pump off, ? hrs. Flow off, ? hrs.
Flow off, ? hrs.
Increased B.O.D. feed by 50%
co
-------
APPENDIX B-3: page 2 of 10
DATE
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31 -
4-1
2
3
4
5 ;';"
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm
Q
-r-l 4J
nl flj
• i
U AJ 3
tLj 'ri llj
**j ^ *^
* w
.
z
w
QJ
4-*
J
Additives,
Working Solutions
•« «i
M n3
a c
00 j3
(A P-
'
'
U)
01 tt)
at .u
W .H
CO i-l
(d 1-1
1— 1 !— 1
o •-<
S 'rf
E
- .
« •
U ta
(U ^
CO 00
3
V
M .
PQ C
•H
•Q E
"^
[14 £
Mixed Liquor
Ft
e
•— i
O "
ca d
CO ,
O
—•
••- 0 ft
...
W "*».
O «-•
js e
&
6.0
2.6
2.0
1.5
4.0
5.0
1.3
.8
1.0
2.0
2,5
5.0
6.5
3
o
Efl
13 ^-*
01 —
•O Ml
d E
(U
Q,
CO
3
OT
^ 0}
C J2
(0 U
H C
O "
•U to
to TJ
4J Q
C
E J3
•H O
•O o
Q)
-------
APPENDIX B-3:
page 3 of 10
DATE
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5-1
2
3
4
5
6
7
8
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm
c
Q
11 4J
it C
Is ji
*j J? »Tj
*]j r»1
M ix4
••j
ja
n
2
*^
•S
**
Additives,
Working Solutions
u«
ca c
M P
3 O
CO O-
(0
in QJ
(U u
in -H
w »-•
cd ^
r-i ^j
o ^
S *^
g
i-i M
<1) i-H
kJ ffl
d 60
u
g c
•r-4
13 €
D *••*„
y ^^
^ €
Mixed Liquor
ft.
0)
a
(0
e
PH
O -
CO C
V) Q
*^ &0.
Q ^\
M
0
r-
cu
o v
O 4J
JJd
O r-*
J= E
^3
20.0
14.0
1.25
2.0
3.0
.05
1.25
2.5
2.0
4.0
2.5
.5
.3
2.5
2.5
UJ
•X)
•l-l
o
CO
•a ^
It
V
a.
tn
D
en
220
200
240
210
180
240
w
e
(0
H
C
•H
m
d
1
^^
*O
Q)
en en
2 1/2
4
9
4
4
4
3
3 1/2
3 1/2
3
4
3
3
3
3 1/2
3
3
3 1/2
3 1/2
3 1/2
3
3
3
2
3
3
2
3
RETURN
SLUDGE
*i
01
c
0 n ,
iw £'
4-1 v-t
O ^"^
rC •""*
£ £
1*4
35.0
26.0
2.50
2.0
2.0
3.0
1.5
3.0
7.0
7.5
1.5
1.0
.5
3-5
3.0
op
B
TJ
~C %
0> -H
a. —i
en o
3 en
en
SPECIAL
CONDITIONS
CO M
0 0
^ u
O flJ
fTT| p^
X
00
m (Jj
60 i-l
•a ^
•3 ^*^
T— ( ^
to ffl
a
S
60 «
e .-i
« °
rt v
O 00
•-I *O
fa 3
^^
cn
X
X
OPERATIONAL NOTES
Rising sludge noted during Imhoff cone
test
Recycle pump off, ? hrs.
Recycle pump off, ? hrs.
Molasses feed off, ? hrs.
Sludge recycle, 1 gpm; losing solids from
clarifier
ncr eased molasses from 1500 ml to 3000 ml
Ul
-------
APPENDIX B-3: page 4 of 10
DATE
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
6-1
2
3
4
5
6
7
8
9
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm
4-1
G
< 01
4J 3
IS
vu
z
-
**
01
3
;
Additives,
Working Solutions
A (Q
kt "O
4 C
10 a
10
4 0
Mixed Liquor
h
0)
3
td
K
H
86
88
90
91
88
87
88
84
80
84
86
87
87
86
88
85
86
90
84
89
87
91
86
85
82
84
84
85
86
88
88
CM
O
r-t
> e
o »
m C
w at
SK
X
o
.1
.2
.2
.1
.2
a" n
o w
CJ 4J
1^4 ^^|
1-1 "^
|1
M
5.2
6.0
.031
6.0
3.5
3.5
1.5
5.0
2.0
3.0
2.5
5.5
3.5
4.5
1.0
.7
.7
-
do
E
210
110
140
60
110
80
Tl
C
O *
u o)
C
V -H
•*4 -0
"O U
l> a>
CO CO
3
4
4 1/2
3
2 1/2
3
4
3
3
3
3
4
3 1/2
31/2
4
4 1/2
2
3
3
2 1/2
2 1/2
1 1/2
3
2
2
2
2
RETURN
SLUDGE
•
c
O M
U Hi
4J
•W **4
o *-.
€ E
H
2.0
1.0
11.0
4.5
5.5
1.5
2.0
13.0
3.0
15.0
2.5
.6
•o
0) *
-a a,
c -o
O. ~<
a o
3 en
OT
SPECIAL
CONDITIONS
60 14
C O
H t)
g 8
fe fid
bO
at c
DO -H
3 r-4
^ d
vi pa
M
o>
S
14
g-5
•* cj
<0 at
E'I 3
— ^
la
X
OPERATIONAL DOTES
Baffle installed in clarifier
Floating solids
Power off 4O min.
Skimmer installed on clarifier; sludge
recycle, 1/2 gpm.
Recycle pump off, ? hrs.
-
Bad odor
Normal operation
Dark color, bad odor
Recycle pump off, ? hrs.
-------
APPENDIX B-3: page 5 of 10
DATE
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
7-1
2
3
4
5
.6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
BIOLOGICAL REAC.TOR
Influent '.
Flow Rates,
gpm
:riftcaUc
Unit
Effluent.
z
Water
Additives,
Working Solutions •
- to
I- T3
(0 C
do 3
3 O-
w (X
«
Molasses,
illiliter
£
U tn
Q> _t
U (0
SM
o
u
Sc
*$
o> — •
b E
Mixed Liquor
CM
«
0)
emperatur
H
88
90
91
93
92
92
92
92
92
90
92
92
92
93
90
91
90
93
92
93
93
91
93
92
92
92
90
92
91
91
95
92
93
91
91
91
93
92
92
92
91
cf
!~l
^ "^ ;
Dissolve
xygen, mg
o
.1
3.0
.2
1.0
.5
1.3
..
.2
.2
.2
.2
.2
8\
Imhoff Co
ml/lite
.8
.7
.7
.4
.3
.5
1.0
2.0
1.0
.5
1.0
.7
.5
.5
1.0
1.0
1.25
.2
.3
.5
1.0
1.0
(O
•o
•r-J
O ,
CO
•a -*
01 -*.
1 %
a.
U)
3
O3
.M fl
1
c
O "
•H
ij
Sedimenta
Secchi Di
2 -
1 1/2
2 1/2
2 1/2
3 1/2
4
5
4
4
3
3
3
4
31/2
4
4
3
4
4 1/2
3 1/2
4
4
4
4
4
3
3
3
4
4
3
4
4
3
3
3
3
3
RETURN
SLUDGE
u
mhoff Con
ml/liter
HI
3.0
1.1
.8
5.5
6.5
2.0
.7
2.5
1.0
.5
1.0
2.0
1.2
^
'
00 .
uspended
Solids, in
CO
SPECIAL
CONDITIONS
Foami ng
Reactor
Sludge
Bulking
Vf
0)
•H
*M
i-l
Floating
udge Clar
.— i
CO
X
OPERATIONAL NOTES
-------
APPENDIX B-3: page 6 of 10
DATE
21
22
23
24
25
26
27
28
29
30
31
8-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpro
c
O
i-i JJ
T* Jji
Q V
O 4J 3
fl •*< i-4
«M C M4
•H » «W
H H
4J
•v4
s
5
Additives,
Working Solutions
si
!?§
en a
to
•« Vi
SO)
.u
CO vi
r-< **
O i-4
3000
3000
3000
3000
3000
3000
3000
3000
3000
3000
3000
f
^4
0 -
to e
(0 41
•H 00
°l
.2
3.1
.4
.2
.7
.02
.7
0)
C M
O 01
U «J
p
1.0
1.0
6.0
3.0
2.0
10.0
1.3
.5
6.0
1.0
.3
1.0
15.2
5.0
3.5
3.0
3
_,
^i^
,f
H C
•H
e
o *
•H U
4J to
a -H
4J O
e
Sedime
Secchi
4
3
3 1/2
3
4
4
3
2 1/2
3 1/2
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
4
3
10
13
2
2
2
2
3 1/2
RETURN
SLUDGE
w
e
O b
O V
4J
M-l v4
o •*-.
3 -a
2.5
3.0
7.5
4.0
20.0
1.2
.6
1.0
20.0
.3
2.5
70.0
20.2
15.3
11.0
•^
•0
ty •»
C TJ
O. r-4
(a O
3 en
SPECIAL
CONDITIONS
tiQ I*
"s o
1 1
00
V C
tlO -H
•o ^
y -•
en pa
X
5
5
00 «
e -4
nj a)
CO
X
OPERATIONAL NOTES
Waste flow off, ? hrs.
Molasses pump off, 4 hrs.
Intermittent flow rate of molasses
;Bad odor
00
-------
APPENDIX B-3: page 7 of 1O
DATE
27
28
29
30
31
9-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
10-1
2
3
4
5
6
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpro
a
A
:rificatic
Unit
E-f'fluent
,
2
U
V
$
Additives,
Working Solutions
- en
(0 C
00 3
3 0
to a
(0
Molasses,
IHiliter
g
3000
3OOO
3008
0) -4
l^
V
£<:•
"1
I£'E
150
150
150
Mixed Liquor
h
•h
emperatur
E-t
89
88
90
90
9O
90
87
92
93
92
98 .-5
92
92
93
93
92-
92
92
92
93
94
92
93
94
92
94
89
92
90
87
82
83
85
84
86
88
89
90
92
0N
13 -•*
Dissolve
xygen, mg
o
.1
1.0
1.0
0)
C h
33
J 1
2.5
2.0
2.0
2.5
0.2
3.5
1.0
1.5
5.0
5.5
9.5
2.5
3
4.5
3
4
CO
•o
O
VI
Tl ^
10
3
M 1)
C
O **
•r4 U
4J «
Sedimenta
Secchi Di
2 1/2
3
3
3
- 3
3
2 1/2
- 3
. 3
3
3
3
2 1/2
3 1/2
3
3
6
3
3
2
3
3
2
2
2
2
2
3
2
2
2
2
2
2
2
RETURN
SLUDGE
Of
e
o »*
u s
«M -H
>t4 t-l
O ^
£ — * '
E e
3.0
5.4
6.0
4.5
11.0
4.0
2.5
10.0
10.0
20.5
20.0
15. 0
23.0
20.0
15.0
00
uspended
Solids, m
W)
SPECIAL
CONDITIONS
Foaming
Reactor
Sludge
Bulking
X
X
X
•ft
M *
C ft
.-1 •«
fc 3
i— i
CO
OPERATIONAL NOTES
VO
-------
APPENDIX B-3: page 8 of 10
DATE
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
11-1
2
3
4
5
6
7
8
9
10
11
12
13
14 -
BIOLOGICAL REACTOR
Influent
Flow Rates,
gp
g
O
•n 4J
*~ ~
tg V
O -U 3
£ £ £
1j ^"l
M uu
-r4
Z
n
Q)
4J
•?
>J
Additives,
Working Solutions
* to
iJ "O
CQ C
00 3
3 0
M O-
(0
U1 0)
V 4J
01 -rJ
« 1-1
(Q *r4
• ,—1 ,_<
O •— i
JEJ »p^
£
4500
4500
l-i tfl
0) _4
4-) IB
^E
40
Ol
w! c
-o 'e
«--,
01 — i
Mixed Liquor
fa
V
3
td
0.
S
01
(H
89
92
79
78
82
82
83
83
84
80
78
78
80
82
80
84
85
82
85
86
90
82
76
76
75
80
80
72
70
69
71
78
83
83
78
76
78
76
75
CM
O
.-1
x: — .
f^f
S c
to at
••-* 00
Q X
O
.1
.1
.3
.1
.7
.15
.8
.15
.15
.5
.48
2.7
.16
.33
.24
1.69
01
O 01
O 4J
jj<
° •g
g
w
2.5
2
2
5
1.5
10.0
5.0
5.0
.2
6.0
9.0
8.0
2.5
9.0
2.5
1.3
.7
.5
.3
.9
^
^^
1°
a.
1 1
c
o *
4J ta
C
(I) -r4
^H O
*o o
U V
co cn
2
2 1/2
2
2
1 1/2
2
2
2
2
1 1/2
1 1/4
2
2
2
2
2
1 1/2
2
2 1/2
2
2
3
2 1/2
2 1/2
2 1/2
3
2
2
2
RETURN
SLUDGE
«
£
O M
O V
o •*-
A ~l
E 6 •
M
13.0
3.5
10.0
3.0
30.0
15.0
5.0
23.0
20.0
40.0
10.0
10.5
*•?
2.0
1.2
.7
1.5
00
B
to
G -a
0) -r4
CL r-l
CO O
3 CO
en
SPECIAL
CONDITIONS
op w •
d o
•H 4J
£ o
gtfl
0)
Frf ^V*
X
X
X
bD
QJ C
M -H '
»— < 3
cn PQ
X
X
X
X
X
X
X
X
X
•2
•H
w ta
c: -*
^ o
4J
CO CD
O 60
^-1 -O
ptf 3
^*
Ul
OPERATIONAL NOTES
Nate molasses change
Color change, light to dark
-------
APPENDIX B-3: page 9 of 10
DATE
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12-1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm
c
5 u
M a
SO)
u 3
t4 •* ^
>*4 B *W
•^0*4
w u
14
as
Water
Additives,
Working Solutions
» 01
$"8
2§
tn a
<0
Molasses,
illtllter
B
4500
4500
3000
4500
4500
u to
W *-4
gS
V
*J
3c
T*
•S4
V ^
b. E
150
Mixed Liquor
In
01
emperatur
H
71
65
73
78
79
80
78
81
77
67
66
77
79
81
84
80
83
85
86
86
84
84
76
79
81
82
83
72
72
69
74
78
76
80
80
82
83
ol
O
d
B *^.
Dissolve
xygen, mg
o
.16
.30
.38
.98
.8
.2
.3
.5
.8
.34
.79
.1
.5
.14
.7
.1
.15
.16
- .1
.14
g M
Imhoff Co
ml/lite
4.0
15.0
3.0
4.5
.7
.3
.5
4.5
.5
1.2
.7
.8
2.0
1.0
.7
2.5
.7
3.0
2.5
3.0
"2.5
1.0
•5
ft
O
M
•o ^
u --^
ft
ID
3
CO
160
70
120
110
B*
n o
H B
fl
C
O *
•^ 0
«
-------
APPENDIX B-3: page 1O of 10
DATE
23
24
25
26
27
28
29
30
31
1-1-71
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
BIOLOGICAL REACTOR
Influent
Flow Rates,
gpm
c
Q
.1. m
O 4J 3
*H ED tw
M b]
Z
' n
1
Additives,
Working Solutions
* to
ft) C
60 3
=J O
CA O.
CO
w1 o!
01 x>
CO -H
Vt i-l
(Q -^
•H i— <
O i-«
0
h
-------
APPENDIX^
Alkalinity is defined as the capacity of a water to neutralize acid.
For most waters, this ability can be expressed by the equation
Alkalinity, mg/1 CaCC>3 - 50,000(2[C03=] 4- [HC03~] + [Olf] - [H+]) (1)
where [ ] represents molar concentrations. The purpose of the discussion
is to propose a reaction scheme for nitrification and from this scheme
calculate potential alkalinity requirements for the process. Verifica-
tion of the proposed chemical mechanisms will be attempted by making an
alkalinity balance on the system which includes, in addition to the
biochemical reactions, the supplemental alkalinity intentionally added
to the system. In order to accomplish this calculation, the sources and
changes in carbonate, bicarbonate, hydroxide, and hydrogen ions must be
known or estimated.
The principal reactions taking place within the nitrification unit are
the oxidation of ammonia to nitrite and nitrite to nitrate. These two
reactions can be represented by the following equations:
Nil,"*" + 2H20-»— NO ~ + 8H+ + 6e~ . (2)
and ,
NO + 2H + 2e~ (3)
As can be seen, these reactions produce hydrogen ions which are negative
alkalinity. These reactions also produce electrons (oxidation) and must
be accompanied by simultaneous reactions which utilize electrons (reduc-
tion) . Two reductive reactions knox-m to occur during nitrification in-
volve oxygen and the utilization of inorganic carbon by the autotrophic
bacteria to produce biological cell material. The reduction of oxygen
is often represented chemically as
02 + 2H20 --9- 40H~ - 4e~
The reduction of inorganic carbon, which in this case is present mostly
as bicarbonate, to organic carbon is given by equation (5).,
s
HCO ~ + 3H 0 -*— CH 0 + 50H~ - 4e~ (5)
•J ^ 2, :
173
-------
The hypothetical product, CI^O, was chosen because it closely approxi-
mates chemically the composition of cellular organic carbon. Reactions
4 and 5 produce hydroxide ions which add to the alkalinity but bicarbonate
is used in reaction (5) which tends to lower it.
Test data is available which allows at best some approximation of the
contribution of reactions (1), (2), and (4) to be made fairly directly.
Unfortunately no direct measure of the amount of oxygen utilized in the
process was possible. The amount of oxygen utilized can be made in-
directly through the use of an oxidation-reduction balance. In other
words, the electrons released in reactions (2) and (3) and not utilized
by (5) will be assigned to reaction (4) , the reduction of oxygen.
To use an oxidation- re duct ion computation requires the assumption that
all significant reactions are known. This assumption is believed to be
reasonably valid. Oxidation-reduction balances are best made using the
concentration units of equivalents per liter, epl. From the data
available, nitrite production, according to reaction (2) , was best
estimated from the change in ammonia concentration through the unit.
Nitrite could not be used directly since the influent was not monitored
regularly for this constituent, and variable amounts may well have been
present. In addition, some nitrite was converted on to nitrate within
the unit. The equivalents per liter (epl) of nitrite produced within
the unit is given in equation (6) .
epi(N02-N) = [CJCNH.J-N) - cE(NH3-N)] 14p00 (6)
where ,
epl(NO~ -N) « equivalents per liter of nitrite nitrogen,
Cj.CNH.j-N) = influent NH3 as mg/1 - N, and
C£(NH3-N) - effluent NH3 as mg/1 - N.
The factors of 6 and 14000 are, respectively, the electrons released per
molecule of nitrite formed or equivalents per mole and the milligrams of
nitrite nitrogen per gram mole.
The equivalents of nitrate produced can be estimated directly from the
change in concentration of nitrate in the unit. From the stoichiometry
of reaction (3) , this can be written as
epl(N03N) - [CS(N03"-N) - C^NO^-N)] QQ (7)
174
-------
The reduction of inorganicicarbon according to equation (5) cannot be
evaluated from alkalinity measurements for obvious reasons. The alter-
native is to estimate this reduction through the increase in organic
content of the effluent. Two alternate techniques were utilized during
the test to monitor this parameter. During the first phase of the ex-
periment, organic Carbon measurements were made and the oxidation-reduc-
tion statement using organic carbon (DC) becomes
j
epKHCO ") = [C (OC) - C (OC)J 4_ (8)
12000
The second part of the test was monitored using chemical oxygen demand
and the statement using this parameter is
epl(HCO ~) - [C (COD) - C (COD) ] 4 (8a)
X 32000
The use of either of these methods is not entirely satisfactory as
undoubtable losses of these materials occur through normal aerobic
biochemical mechanisms and possibly through denitrification in the unit
and its sedimentation facility.
The oxygen requirement can be calculated using the fact that the equivalents
oxidized must equal equivalents reduced which is
epl(oxidized) = epl(reduced) (9)
epl(N02~-N) + enl(N03~-N) = epl(HC03~) + epl(02> (10)
or
Substituting and reducing equations (6), (7), and (8) gives the oxygen
requirement in terms of mg/1 of 02
') L 3 — 3 A
2 7 ' * '3 7 3 3
for those periods when organic carbon measurements were made and for
those periods when chemical oxygen demand was used.
02 = -j [AC(H!I3-N)] + - [AC(N"03~-N)J - Ac(COD) (lla)
•' 0 "
where C indicates the change in concentration
175
-------
The numerical solutions for equations (11) and (lla) for those periods
of relatively good nitrification are given in Table C-l. These tabulated
results indicate the large amounts of oxygen required by the nitrification
unit.
This estimate of oxygen utilization now allows the computation of the
alkalinity changes that might be expected during nitrification. Using
the definition of alkalinity, equation (1), and the stoichiometry of the
major assumed reactions given by equations (2), (3), (4), and (5), the
following equations can be derived for alkalinity changes in terms of
rag/1 CaCO :
(1) Nitrite production -
Alkalinity utilized - 50,000 [AC(NH.-N)] 8
3 ~T4000~~
(2) Nitrate production -
Alkalinity utilized = 50,000 [Ac(NO ~-N) ] _ 2_ __ (13)
4 " 14000
(3) Inorganic carbon reduction -
(a) For organic carbon
Alkalinity produced = 50,000 [Ac(OC)] _ 5_ _ (14)
12000
(b) For chemical oxygen demand
Alkalinity produced - 50,000 [^(OC)] __ 5 _ (14a)
3~2000
(4) Oxygen utilization -
Alkalinity produced = 50,000 [CO ] __ 4 _ (15)
32000
The results of each of these alkalinity changes is tabulated in Table C-l.
In addition, the algebraic summation of these changes is also given under
the column entitled total potential alkalinity utilized. The require-
ment for alkalinity up to 4500 mg/1 must be satisfied or the process will
be self-limiting because of low pH and the lack of inorganic carbon. The
alkalinity requirement to nitrify the entire waste stream would be very
large. In the pilot plant, this alkalinity requirement was met by allowing
a decrease in alkalinity through the unit and by addition of soda ash
and sodium hydroxide. The total of these alkalinity sources is given in
the table.
The difference between the calculated alkalinity utilized, and the alka-
linity accounted for by artificial additions and changes in residual alka-
linity of the waste are also tabulated as both absolute amounts and as a
176
-------
APPENDIX C
TABLE C-l: Nitrification Unit. Alkalinity Balance for Selected Sampling Periods
Period
138-144
145-151
222-228
229-235
257-263
264-270
306-312
313-319
327-333
Ammonia
mg/1 N
4J
jj
o
T—l
C
t-t
430
430
580
670
490
520
49O
41O
280
, ,
g
•w
>M
W
120
50
330
380
50
130
110
80
50
U
1
310
380
250
290
440
39O
380
330
230
Nitrate
mg/1 N
t t
y*
0
»H
C
1-4
O
0
0
0
0
0
o
o
0
4J
0
tw
* O e*>
4-1 C O
-rf 0) o
c a.
-------
percentage of the alkalinity utilized. This analysis tends to show that
alkalinity changes could not be predicted consistently using the reactions
involving the oxidation of ammonia to nitrite and nitrate, the reduction
of oxygen, and the conversion of inorganic to organic carbon and the
monitored data from the experiment. Whether these differences result from
assuming an inadequate chemical description of the process or from inade-
quate data is not known. In large measure, however, these differences
may not be unreasonable considering the large multiplication factors
applied to a rather limited number of analyses on grab samples in the con-
version of these constituents to oxidation-reduction equivalents and to
alkalinity equivalents. In addition, these potential discrepancies are
magnified through two substractions involved in the computations.
•'« AU.S. GOVERNMENT PRINTING OFFICE: 1973 514-154/256 13
-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
1. Report No.
w
7/i Biological Removal of Carbon and Nitrogen Compounds 5'. Deport Date
from Coke Plant Wastes 6. .
, s.
A t-ior(s) -Barker, -John E.; Thompson, R., J.; Samples, w. R.;
McMichael, E. C.
iron and Steel Institute
150 East 42 Street
New York City, New York 10017
Report No.
10. Pttijet.-t.ifi'
12010 EDY
11 Contract/Grant fie
\13.-~ Type t,.f Report and-
Period Covered
• p/eitienfary Note'
Environmental Protection Agency report
number, EPA-R2-73-167, April 1973.
16. -4/i.s tract
A one-year study of a biological process for treatment of coke plant ammonia
liquor was conducted. The process was designed to remove carbon compounds and
ammonia. The pilot plant consisted of three treatment systems arranged in series.
These systems were designed for the removal of carbon compounds, the oxidation
of ammonia to nitrate (nitrification), and the reduction of nitrate to nitrogen
gas (denitrification). The study was jointly sponsored by the American Iron and
Steel Institute, the Environmental Protection Agency, and Armco Steel Corporation.
The results of the study indicate that the biological process can be used
to remove carbon compounds and ammonia from dilute ammonia liquor. Treatment
efficiencies obtained include removals of greater than 99.9 percent phenol,
80 percent COD, and 90 percent ammonia. Removal efficiencies for cyanide and
thiocyanate were less encouraging with averages of 57 and 17 percent, respectively.
.(Myers - RSKERL)
17a. Descriptors
Group 16 (VABC) Aerobic Conditions, Anaerobic Condition, Biochemical Oxygen
Demand, Heated Water, Industrial Wastes, Nitrogen Compounds, Organic Matter,
Phenols, Water Pollution Sources.
17b. Identifiers
Coke Plant wastes, Ammonia Liquor, Nitrification, Denitrification, Carbon Com-
pound, Ammonia, Cyanide, thiocyanate, Phenol, State-of-the-Art, Aeration Time,
Problem areas, Sludge bulking, Activated Sludge, Pilot Plant.
17c. COWRR Field & Group
18. A \-ailability
39.'' ^Security das's.
•. . : :•• '(Report) . • ..' •
*fl. Security Cfrss,
. ' (P*JSe) •'• '
•21.' No. of
Pages
i 22. Ptiee
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 2O24O
Leon H. Myers
in* tiiuiioiRobert S. Kerr Environment i Research Lab.
-------
|